Condensed heteroclyclic compounds and pesticides

ABSTRACT

To provide novel pesticides, especially insecticides or acaricides. 
     A condensed heterocyclic compound represented by the formula (1) or its salt, or N-oxide thereof: 
     
       
         
         
             
             
         
       
     
     wherein Q is a structure represented by Q1, Q2 or the like, D substituted with —S(O) n R 1  is a structure represented by D1 or D2, A 1  is N(A 1a ) or the like, A 1a  is C 1 -C 6  alkyl or the like, A 4  is a nitrogen atom or C(R 4 ), A 5  is a nitrogen atom or C(R 5 ),
         R 1  is C 1 -C 6  alkyl or the like, each of R 2 , R 5  and R 6  is independently a hydrogen atom or C 1 -C 6  alkyl, each of R 3 , R 4 , Y1, Y2, Y3 and Y4 is independently a halogen atom, halo (C 1 -C 6 ) alkyl or the like, and n is an integer of 0, 1 or 2.

TECHNICAL FIELD

The present invention relates to a novel condensed heterocyclic compoundand its salt, and a pesticide containing the compound as an activeingredient.

BACKGROUND ART

Patent Documents 1 to 31 disclose various condensed heterocycliccompounds, however, they failed to disclose the condensed heterocycliccompounds of the present invention. Usefulness of the condensedheterocyclic compounds of the present invention as pesticides,especially, as insecticides, acaricides or parasiticides againstinternal or external parasites in or on a mammal, fish or bird is notdisclosed at all.

PRIOR ART DOCUMENTS Patent Documents

Patent Document 1: WO2016/005263

Patent Document 2: WO2015/198859

Patent Document 3: WO2015/133603

Patent Document 4: WO2015/121136

Patent Document 5: WO2015/091945

Patent Document 6: WO2015/087458

Patent Document 7: WO2015/071180

Patent Document 8: WO2015/059088

Patent Document 9: WO2015/002211

Patent Document 10: WO2015/000715

Patent Document 11: WO2014/157600

Patent Document 12: WO2014/148451

Patent Document 13: WO2014/142292

Patent Document 14: WO2014/132972

Patent Document 15: WO2014/132971

Patent Document 16: WO2014/123206

Patent Document 17: WO2014/123205

Patent Document 18: WO2014/104407

Patent Document 19: WO2013/180194

Patent Document 20: WO2013/80193

Patent Document 21: WO2013/191113

Patent Document 22: WO2013/191189

Patent Document 23: WO2013/191112

Patent Document 24: WO2013/191188

Patent Document 25: WO2013/018928

Patent Document 26: WO2012/086848

Patent Document 27: WO2012/074135

Patent Document 28: WO2011/162364

Patent Document 29: WO2011/043404

Patent Document 30: WO2010/125985

Patent Document 31: WO2009/131237

DISCLOSURE OF INVENTION Technical Problem

With the advance of development of pesticides targeted at various pestinsects such as agricultural pest insects, forest pest insects orhygienic pest insects, various pesticides have been put into practicaluse.

However, recently, control of pest insects with conventionalinsecticides or fungicides has become difficult in more and more cases,as pest insects acquire resistance to them over many years of their use.Problems of the high toxicity of some conventional pesticides and of thedisturbance of the ecosystem by some conventional pesticides whichremain in the environment for a long period are becoming apparent. Underthese circumstances, development of novel pesticides with highpesticidal activity, low toxicity and low persistence is alwaysexpected.

It is an object of the present invention to provide a novel pesticidewhich has excellent pesticidal activities, which has low toxicity, forexample, which has little harmful effect on non-target organisms such asmammals, fishes and useful insects, and which has low persistence.

Solution to Problems

The present inventors have conducted extensive studies to achieve theabove object and as a result, found that a novel condensed heterocycliccompound represented by the following formula (1) of the presentinvention is a very useful compound which has excellent pesticidalactivities particularly insecticidal and acaricidal activities, andwhich has little harmful effect on non-target organisms such as mammals,fishes and useful insects, and accomplished the present invention.

That is, the present invention relates to the following [1] to [95].

[1] A condensed heterocyclic compound represented by the formula (1) orits salt, or N-oxide thereof:

wherein Q is a structure represented by Q1, Q2, Q3, Q4, Q5 or Q6:

D substituted with —S(O)_(n)R¹ is a structure represented by D1 or D2:

A¹ is N(A^(1a)), an oxygen atom or a sulfur atom,

A⁴ is a nitrogen atom or C(R⁴),

A⁵ is a nitrogen atom or C(R⁵),

A⁸ is a nitrogen atom or C(R⁸),

R¹ is C₁-C₆ alkyl or halo (C₁-C₆) alkyl,

each of R², R⁵, R⁶ and R⁸ is independently a hydrogen atom or C₁-C₆alkyl,

each of R³, R⁴ and R⁷ is independently a hydrogen atom, a halogen atom,halo (C₁-C₆) alkyl, halo (C₁-C₆) alkylthio, halo (C₁-C₆) alkylsulfinylor halo (C₁-C₆) alkylsulfonyl,

each of Y1, Y2, Y3 and Y4 is independently a hydrogen atom, a halogenatom, C₃-C₆ cycloalkyl, (C₃-C₆) cycloalkyl optionally substituted withY^(a), C₁-C₆ alkyl, halo (C₁-C₆) alkyl, C₁-C₆ alkoxy, halo (C₁-C₆)alkoxy, C₁-C₆ alkylthio, halo (C₁-C₆) alkylthio, C₁-C₆ alkylsulfinyl,halo (C₁-C₆) alkylsulfinyl, C₁-C₆ alkylsulfonyl, halo (C₁-C₆)alkylsulfonyl, —NH₂, —NHR^(90g), cyano, nitro, G1 or G2,

R^(90g) is C₁-C₆ alkyl, halo (C₁-C₆) alkyl, C₁-C₆ alkylcarbonyl, halo(C₁-C₆) alkylcarbonyl, C₁-C₆ alkoxycarbonyl, halo (C₁-C₆)alkoxycarbonyl, C₁-C₆ alkylsulfonyl or halo (C₁-C₆) alkylsulfonyl,

G1 is a structure represented by G1-1, G1-2, G1-3 or G1-4:

G2 is a structure represented by G2-1, G2-2, G2-3 or G2-4,

A^(1a) is a hydrogen atom or C₁-C₆ alkyl,

each of Z¹ and Z² is independently a halogen atom. C₁-C₆ alkyl, halo(C₁-C₆) alkyl, C₁-C₆ alkoxy, halo (C₁-C₆) alkoxy, C₁-C₆ alkylthio, halo(C₁-C₆) alkylthio, C₁-C₆ alkylsulfinyl, halo (C₁-C₆) alkylsulfinyl,C₁-C₆ alkylsulfonyl, halo (C₁-C₆) alkylsulfonyl, cyano or nitro, whenp2, p3, p4 or p5 is an integer of at least 2, each of Z¹ and Z² may beidentical with or different from one another,

Y^(a) is cyano, —C(O)OH or —C(O)NH₂,

p2 is an integer of 0, 1 or 2,

p3 is an integer of 0, 1, 2 or 3,

p4 is an integer of 0, 1, 2, 3 or 4,

p5 is an integer of 0, 1, 2, 3, 4 or 5, and

n is an integer of 0, 1 or 2.

[2] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [1], wherein the formula (1) is represented bythe formula (1-1):

wherein R¹ is C₁-C₆ alkyl, and A^(1a) is C₁-C₆ alkyl.[3] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [2], wherein each of R², R⁴ and R⁵ is a hydrogenatom, R³ is halo (C₁-C₆) alkyl, halo (C₁-C₆) alkylthio, halo (C₁-C₆)alkylsulfinyl or halo (C₁-C₆) alkylsulfonyl, Y1 is a hydrogen atom or ahalogen atom, and each of Y2, Y3 and Y4 is independently a hydrogenatom, a halogen atom, halo (C₁-C₆) alkyl, C₁-C₆ alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆ alkylsulfonyl, G1 or G2.[4] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [3], wherein A⁴ is C(R⁴), A⁵ is a nitrogen atom,R³ is halo (C₁-C₆) alkyl, halo (C₁-C₆) alkylthio or halo (C₁-C₆)alkylsulfinyl, Y2 is a hydrogen atom, a halogen atom, halo (C₁-C₆)alkyl, C₁-C₆ alkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ alkylsulfonyl or G1,Y3 is a hydrogen atom, a halogen atom, halo (C₁-C₆) alkyl or G2, Y4 is ahydrogen atom, G1 is G1-1, G2 is G2-2, Z² is halo (C₁-C₆) alkyl, p3 isan integer of 1, p5 is an integer of 0, and n is an integer of 0 or 2.[5] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [3], wherein A⁴ is a nitrogen atom, A⁵ is C(R⁵),R³ is halo (C₁-C₆) alkyl, Y3 is a hydrogen atom or a halogen atom, eachof Y2 and Y4 is a hydrogen atom, and n is an integer of 0 or 2.[6] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [1], wherein the formula (1) is represented bythe formula (1-3):

wherein A⁴ is a nitrogen atom, A⁵ is C(R⁵), R¹ is C, —C, alkyl, each ofR² and R⁵ is a hydrogen atom, R³ is halo (C₁-C₆) alkyl, Y1 is a hydrogenatom or a halogen atom, each of Y2, Y3 and Y4 is independently ahydrogen atom, a halogen atom, halo (C₁-C₆) alkyl, C₁-C₆ alkylthio,C₁-C₆ alkylsulfinyl, C₁-C₆ alkylsulfonyl, G1 or G2.[7] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [6], wherein R⁶ is a hydrogen atom, each of Y1,Y3 and Y4 is a hydrogen atom, Y2 is halo (C₁-C₆) alkyl, and n is aninteger of 2.[8] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [1], wherein the formula (1) is represented bythe formula (1-4):

wherein As is a nitrogen atom, R¹ is C₁-C₆ alkyl, R⁷ is halo (C₁-C₆)alkyl, Y1 is a hydrogen atom or a halogen atom, each of Y2, Y3 and Y4 isindependently a hydrogen atom, a halogen atom, halo (C₁-C₆) alkyl, C₁-C₆alkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ alkylsulfonyl, G1 or G2.[9] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [8], wherein R^(e) is a hydrogen atom, each ofY1, Y3 and Y4 is a hydrogen atom, Y2 is halo (C₁-C₆) alkyl, and n is aninteger of 2.[10] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [1], wherein the formula (1) is represented bythe formula (1-2):

wherein R¹ is C₁-C₆ alkyl, and A^(1a) is C₁-C₆ alkyl.[11] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [10], wherein A⁴ is C(R⁴), A⁵ is a nitrogen atom,R³ is halo (C₁-C₆) alkyl, Y3 is a halogen atom, halo (C₁-C₆) alkyl, —NH₂or nitro, each of R², R⁴, Y1, Y2 and Y4 is a hydrogen atom, and n is aninteger of 0 or 2.[12] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [10], wherein A⁴ is a nitrogen atom, A⁵ is C(R⁵),each of R³ and Y3 is independently halo (C₁-C₆) alkyl, each of R², R⁵,Y1, Y2 and Y4 is a hydrogen atom, and n is an integer of 0 or 2.[13] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [1], wherein the formula (1) is represented bythe formula (1-6):

wherein A⁴ is C(R⁴), A⁵ is C(R⁵), R¹ is C₁-C₆ alkyl, each of R², R⁴ andR⁵ is a hydrogen atom, R³ is halo (C₁-C₆) alkyl, Y1 is a hydrogen atomor a halogen atom, each of Y2, Y3 and Y4 is independently a hydrogenatom, a halogen atom, halo (C₁-C₆) alkyl, C₁-C₆ alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆ alkylsulfonyl, G1 or G2.[14] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [13], wherein each of Y1, Y3 and Y4 is a hydrogenatom, Y2 is halo (C₁-C₆) alkyl, and n is an integer of 0 or 2.[15] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [1], wherein Q is a structure represented by Q1,and D substituted with —S(O)_(n)R¹ is D1.[16] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [1], wherein Q is a structure represented by Q2,and D substituted with —S(O)_(n)R¹ is D1.[17] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [1], wherein Q is a structure represented by Q3,and D substituted with —S(O)_(n)R¹ is D1.[18] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [1], wherein Q is a structure represented by Q4,and D substituted with —S(O)_(n)R¹ is D1.[19] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [1], wherein Q is a structure represented by Q5,and D substituted with —S(O)_(n)R¹ is D1.[20] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [1], wherein Q is a structure represented by Q6,and D substituted with —S(O)_(n)R¹ is D1.[21] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [1], wherein Q is a structure represented by Q1,and D substituted with —S(O)_(n)R¹ is D2.[22] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [1], [15] or [21], wherein A¹ is N(A^(1a)).[23] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [1], [15] or [21], wherein A¹ is an oxygen atomor a sulfur atom.[24] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [3], [10], [15] to [17], [19]and [21], wherein A⁴ is a nitrogen atom, and A⁵ is a nitrogen atom.[25] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [3], [10], [15] to [17], [19]and [21], wherein A⁴ is C(R⁴), and A⁵ is C(R⁵).[26] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [3], [10], [15] to [17], [19]and [21], wherein A⁴ is a nitrogen atom, and A⁵ is C(R⁵).[27] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [3], [10], [15] to [17], [19]and [21], wherein A⁴ is C(R⁴), and A⁵ is a nitrogen atom.[28] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [1] or [20], wherein A⁴ is C(R⁴).[29] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [1] or [20], wherein A⁴ is a nitrogen atom.[30] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [1] or [18], wherein A⁸ is a nitrogen atom.[31] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to the above [1] or [18], wherein A⁸ is C(R⁸).[32] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [31], wherein R¹ is C₁-C₆alkyl.[33] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [31], wherein R¹ is halo(C₁-C₆) alkyl.[34] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [33], wherein each of R², R⁵,R⁵ and R⁶ is independently a hydrogen atom or C₁-C₆ alkyl.[35] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [34], wherein each of R³, R⁴and R⁷ is independently a hydrogen atom, a halogen atom, halo (C₁-C₆)alkyl, halo (C₁-C₆) alkylthio, halo (C₁-C₆) alkylsulfinyl or halo(C₁-C₆) alkylsulfonyl.[36] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [35], wherein R³ is a hydrogenatom, a halogen atom or halo (C₁-C₆) alkyl.[37] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [35], wherein R³ is halo(C₁-C₆) alkyl.[38] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [35], wherein R³ is halo(C₁-C₆) alkylthio, halo (C₁-C₆) alkylsulfinyl or halo (C₁-C₆)alkylsulfonyl.[39] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [38], wherein R⁴ is a hydrogenatom, a halogen atom or halo (C₁-C₆) alkyl.[40] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [38], wherein R⁴ is a hydrogenatom or halo (C₁-C₆) alkyl.[41] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [38], wherein R⁴ is a hydrogenatom, halo (C₁-C₆) alkylthio, halo (C₁-C₆) alkylsulfinyl or halo (C₁-C₆)alkylsulfonyl.[42] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [41], wherein R⁷ is a hydrogenatom, a halogen atom or halo (C₁-C₆) alkyl.[43] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [41], wherein R⁷ is halo(C₁-C₆) alkyl.[44] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [41], wherein R⁷ is halo(C₁-C₆) alkylthio, halo (C₁-C₆) alkylsulfinyl or halo (C₁-C₆)alkylsulfonyl.[45] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [44], wherein each of Y1, Y2,Y3 and Y4 is independently a hydrogen atom, a halogen atom, C₃-C₆cycloalkyl, (C₃-C₆) cycloalkyl optionally substituted with Y^(a), C₁-C₆alkyl, halo (C₁-C₆) alkyl, C₁-C₆ alkoxy, halo (C₁-C₆) alkoxy, C₁-C₆alkylthio, halo (C₁-C₆) alkylthio, C₁-C₆ alkylsulfinyl, halo (C₁-C₆)alkylsulfinyl, C₁-C₆ alkylsulfonyl, halo (C₁-C₆) alkylsulfonyl, —NH₂,—NHR^(90g), cyano, nitro, G1 or G2.[46] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [44], wherein each of Y1, Y2,Y3 and Y4 is independently a hydrogen atom, a halogen atom, halo (C₁-C₆)alkyl, G1 or G2.[47] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [44], wherein each of Y1, Y2,Y3 and Y4 is independently a hydrogen atom, a halogen atom or halo(C₁-C₆) alkyl.[48] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [44], wherein each of Y1, Y2,Y3 and Y4 is independently a hydrogen atom, G1 or G2.[49] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [44], wherein each of Y1, Y2,Y3 and Y4 is independently a hydrogen atom, —NH₂ or nitro.[50] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [44], wherein each of Y1, Y2,Y3 and Y4 is independently a hydrogen atom, C₃-C₆ cycloalkyl, (C₃-C₆)cycloalkyl optionally substituted with Y^(a), C₁-C₆ alkyl, C₁-C₆ alkoxy,halo (C₁-C₆) alkoxy, C₁-C₆ alkylthio, halo (C₁-C₆) alkylthio, C₁-C₆alkylsulfinyl, halo (C₁-C₆) alkylsulfinyl, C₁-C₆ alkylsulfonyl, halo(C₁-C₆) alkylsulfonyl, —NHR^(90g) or cyano.[51] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [44], wherein each of Y1, Y2,Y3 and Y4 is independently a hydrogen atom, halo (C₁-C₆) alkoxy, halo(C₁-C₆) alkylthio or halo (C₁-C₆) alkylsulfonyl.[52] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [44], wherein each of Y1, Y2,Y3 and Y4 is independently a hydrogen atom, C₃-C₆ cycloalkyl, (C₃-C₆)cycloalkyl optionally substituted with Y^(a), C₁-C₆ alkyl, C₁-C₆ alkoxy,C₁-C₆ alkylthio, C₁-C₆ alkylsulfinyl or C₁-C₆ alkylsulfonyl.[53] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [52], wherein Y1 is a hydrogenatom or a halogen atom.[54] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [52], wherein Y1 is a hydrogenatom.[55] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [52], wherein Y1 is a halogenatom.[56] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [55], wherein Y2 is a hydrogenatom, a halogen atom, halo (C₁-C₆) alkyl, G1 or G2.[57] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [55], wherein Y2 is a hydrogenatom, a halogen atom or halo (C₁-C₆) alkyl.[58] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [55], wherein Y2 is a hydrogenatom, G1 or G2.[59] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [55], wherein Y2 is a halogenatom.[60] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [55], wherein Y2 is halo(C₁-C₆) alkyl.[61] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [60], wherein Y3 is a hydrogenatom, a halogen atom, halo (C₁-C₆) alkyl, G1 or G2.[62] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [60], wherein Y3 is a hydrogenatom, a halogen atom or halo (C₁-C₆) alkyl.[63] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [60], wherein Y3 is a hydrogenatom, G1 or G2.[64] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [60], wherein Y3 is a halogenatom.[65] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [60], wherein Y3 is halo(C₁-C₆) alkyl.[66] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [65], wherein Y4 is a hydrogenatom, a halogen atom, halo (C₁-C₆) alkyl, G1 or G2.[67] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [65], wherein Y4 is a hydrogenatom, a halogen atom or halo (C₁-C₆) alkyl.[68] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [65], wherein Y4 is a hydrogenatom, G1 or G2.[69] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [65], wherein Y4 is a hydrogenatom.[70] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [65], wherein Y4 is a halogenatom or halo (C₁-C₆) alkyl.[71] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [70], wherein G1 is a structurerepresented by G1-1.[72] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [70], wherein G1 is a structurerepresented by G1-2, G1-3 or G1-4.[73] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [72], wherein G2 is a structurerepresented by G2-1.[74] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [72], wherein G2 is a structurerepresented by G2-2, G2-3 or G2-4.[75] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [74], wherein A^(1a) is ahydrogen atom.[76] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [74], wherein A^(1a) is C₁-C₆alkyl.[77] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [76], wherein Z¹ is a halogenatom, C₁-C₆ alkyl, halo (C₁-C₆) alkyl, C₁-C₆ alkoxy, halo (C₁-C₆)alkoxy, C₁-C₆ alkylthio, halo (C₁-C₆) alkylthio, C₁-C₆ alkylsulfinyl,halo (C₁-C₆) alkylsulfinyl, C₁-C₆ alkylsulfonyl, halo (C₁-C₆)alkylsulfonyl, cyano or nitro.[78] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [76], wherein Z¹ is a halogenatom, C₁-C₆ alkyl, halo (C₁-C₆) alkyl, C₁-C₆ alkoxy, halo (C₁-C₆)alkoxy, cyano or nitro.[79] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [76], wherein Z¹ is C₁-C₆alkylthio, halo (C₁-C₆) alkylthio, C₁-C₆ alkylsulfinyl, halo (C₁-C₆)alkylsulfinyl, C₁-C₆ alkylsulfonyl or halo (C₁-C₆) alkylsulfonyl.[80] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [79], wherein Z² is a halogenatom, C₁-C₆ alkyl, halo (C₁-C₆) alkyl, C₁-C₆ alkoxy, halo (C₁-C₆)alkoxy, C₁-C₆ alkylthio, halo (C₁-C₆) alkylthio, C₁-C₆ alkylsulfinyl,halo (C₁-C₆) alkylsulfinyl, C₁-C₆ alkylsulfonyl, halo (C₁-C₆)alkylsulfonyl, cyano or nitro.[81] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [79], wherein Z² is a halogenatom. C₁-C₆ alkyl, halo (C₁-C₆) alkyl, C₁-C₆ alkoxy, halo (C₁-C₆)alkoxy, cyano or nitro.[82] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [79], wherein Z² is C₁-C₆alkylthio, halo (C₁-C₆) alkylthio, C₁-C₆ alkylsulfinyl, halo (C₁-C₆)alkylsulfinyl, C₁-C₆ alkylsulfonyl or halo (C₁-C₆) alkylsulfonyl.[83] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [79], wherein Z² is halo(C₁-C₆) alkyl.[84] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [83], wherein Y^(a) is cyano,—C(O)OH or —C(O)NH₂.[85] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [83], wherein Y^(a) is cyano.[86] The condensed heterocyclic compound or its salt, or N-oxide thereofaccording to any one of the above [1] to [83], wherein Y^(a) is —C(O)OHor —C(O)NH₂.[87] A pesticide containing as active ingredient(s) one or more selectedfrom the condensed heterocyclic compounds and their salts as defined inthe above [1] to [86].[88] An agricultural chemical containing as active ingredient(s) one ormore selected from the condensed heterocyclic compounds and their saltsas defined in the above [1] to [86].[89] A parasiticide against internal or external parasites in or on amammal or bird, containing as active ingredient(s) one or more selectedfrom the condensed heterocyclic compounds and their salts as defined inthe above [1] to [86].[90] The parasiticide according to the above [89], wherein the externalparasites are Siphonaptera or ticks.[91] An insecticide or acaricide containing as active ingredient(s) oneor more selected from the condensed heterocyclic compounds and theirsalts as defined in the above [1] to [86].[92] A soil treatment agent containing as active ingredient(s) one ormore selected from the condensed heterocyclic compounds as defined inthe above [1] to [86].[93] The soil treatment agent according to the above [92], which is usedto treat soil by irrigation.[94] A seed treatment agent containing as active ingredient(s) one ormore selected from the condensed heterocyclic compounds and their saltsas defined in the above [1] to [86].[95] The seed treatment agent according to the above [94], which is usedto treat seeds by dipping.

Advantageous Effects of Invention

The compounds of the present invention have excellent insecticidal andacaricidal activities on many agricultural pest insects, spider mites,internal or external parasites in or on a mammal, fish or bird and havesufficient controlling effect on pest insects which have acquiredresistance to conventional insecticides. The compounds of the presentinvention have little harmful effect on mammals, fishes and beneficialinsects, show low persistence and are environmentally friendly. Thus,the present invention can provide useful novel pesticides.

DESCRIPTION OF EMBODIMENTS

In this specification, definitions and meanings of the following termsare as follows.

The compounds of the present invention can have geometrical isomers suchas E-isomers and Z-isomers, depending on the types of substituents inthem, and the present invention covers both E-isomers and Z-isomers andmixtures containing them in any ratios.

The compounds of the present invention can have optically active isomersdue to the presence of one or more asymmetric carbon atoms or asymmetricsulfur atoms, and the present invention covers any optically activeisomers and any racemates.

Further, the compounds of the present invention can have tautomersdepending on the type of substituents in them, and the present inventioncovers all tautomers and mixtures containing them in any ratios.

Some of the compounds of the present invention can be converted, byordinary methods, to salts with hydrogen halides such as hydrofluoricacid, hydrochloric acid, hydrobromic acid and hydroiodic acid, withinorganic acids such as nitric acid, sulfuric acid, phosphoric acid,chloric acid and perchloric acid, with sulfonic acids such asmethanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonicacid, benzenesulfonic acid and p-toluenesulfonic acid, with carboxylicacids such as formic acid, acetic acid, propionic acid, trifluoroaceticacid, fumaric acid, tartaric acid, oxalic acid, maleic acid, malic acid,succinic acid, benzoic acid, mandelic acid, ascorbic acid, lactic acid,gluconic acid and citric acid, with amino acids such as glutamic acidand aspartic acid, with alkali metals such as lithium, sodium andpotassium, with alkaline earth metals such as calcium, barium andmagnesium, with aluminum, and with quaternary ammonium such astetramethylammonium, tetrabutylammonium and benzyltrimethylammonium.

In the present invention, the N-oxide is a compound having a nitrogenatom constituting the ring in the heterocyclic group oxidized. Aheterocyclic group which may constitute an N-oxide may, for example, bea condensed ring containing a pyridine ring.

“The compound of the present invention represented by the formula (1)”will sometimes be referred to as “the compound (1) of the presentinvention”, and “a compound represented by the formula (1-a)” willsometimes be referred to as “a compound (1-a)”. The same applies toother compounds.

Next, specific examples of each substituent used herein will be givenbelow. n— denotes normal, i—iso, s—secondary, and tert—tertiary.

As a “halogen atom”, a fluorine atom, a chlorine atom, a bromine atom oran iodine atom may be mentioned. Herein, the expression “halo” alsomeans such a halogen atom.

The expression “C_(a)-C_(b) alkyl” herein means a linear or branchedhydrocarbon group containing from a to b carbon atoms such as methyl,ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, tert-butyl,n-pentyl, 1,1-dimethylpropyl or n-hexyl, and those within the designatedcarbon number range are selected.

The expression “halo (C_(a)-C_(b)) alkyl” herein means a linear orbranched hydrocarbon group containing from a to b carbon atoms in whichhydrogen atom(s) on carbon atom(s) are optionally substituted withhalogen atom(s) which may be identical with or different from oneanother if two or more halogen atoms are present, such as fluoromethyl,chloromethyl, bromomethyl, iodomethyl, difluoromethyl, dichloromethyl,trifluoromethyl, chlorodifluoromethyl, trichloromethyl,bromodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2-chloroethyl,2-bromoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2-chloro-2,2-difluoroethyl, 2,2,2-trichloroethyl,2-bromo-2,2-difluoroethyl, 1,1,2,2-tetrafluoroethyl,2-chloro-1,1,2-trifluoroethyl, 2-chloro-1,1,2,2-tetrafluoroethyl,pentafluoroethyl, 2,2-difluoropropyl, 3,3,3-trifluoropropyl,3-bromo-3,3-difluoropropyl, 2,2,3,3-tetrafluoropropyl,2,2,3,3,3-pentafluoropropyl, 1,1,2,3,3,3-hexafluoropropyl,heptafluoropropyl, 2,2,2-trifluoro-1-(methyl)ethyl,2,2,2-trifluoro-1-(trifluoromethyl)ethyl,1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl,2,2,3,4,4,4-hexafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl andnonafluorobutyl, and those within the designated carbon number range areselected.

The expression “C_(a)-C_(b) cycloalkyl” herein means a cyclichydrocarbon group containing from a to b carbon atoms in the form of a3- to 6-membered monocyclic or polycyclic ring which may optionally besubstituted with an alkyl group as long as the number of carbon atomsdoes not exceed the designated carbon number range, such as cyclopropyl,1-methylcyclopropyl, 2-methylcyclopropyl, 2,2-dimethylcyclopropyl,cyclobutyl, cyclopentyl or cyclohexyl, and those within the designatedcarbon number range are selected.

The expression “C_(a)-C_(b) alkoxy” herein means an alkyl-O— group inwhich the alkyl is a previously mentioned alkyl group containing from ato b carbon atoms, such as methoxy, ethoxy, n-propyloxy, i-propyloxy,n-butyloxy, i-butyloxy, s-butyloxy, tert-butyloxy or 2-ethylhexyloxy,and those within the designated carbon number range are selected.

The expression “halo (C_(a)-C_(b)) alkoxy” herein means a haloalkyl-O—group in which the haloalkyl is a previously mentioned haloalkyl groupcontaining from a to b carbon atoms, such as difluoromethoxy,trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy,2-fluoroethoxy, 2-chloroethoxy, 2,2,2-trifluoroethoxy,1,1,2,2,-tetrafluoroethoxy, 2-chloro-1,1,2-trifluoroethoxy or1,1,2,3,3,3-hexafluoropropyloxy, and those within the designated carbonnumber range are selected.

The expression “C_(a)-C_(b) alkylthio” herein means an alkyl-S— group inwhich the alkyl is a previously mentioned alkyl group containing from ato b carbon atoms, such as methylthio, ethylthio, n-propylthio,i-propylthio, n-butylthio, i-butylthio, s-butylthio or tert-butylthio,and those within the designated carbon number range are selected.

The expression “halo (C_(a)-C_(b)) alkylthio” herein means ahaloalkyl-S— group in which the haloalkyl is a previously mentionedhaloalkyl group containing from a to b carbon atoms, such asdifluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio,bromodifluoromethylthio, 2,2,2-trifluoroethylthio,1,1,2,2-tetrafluoroethylthio, 2-chloro-1,1,2-trifluoroethylthio,pentafluoroethylthio, 1,1,2,3,3,3-hexafluoropropylthio,heptafluoropropylthio, 1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethylthioor nonafluorobutylthio, and those within the designated carbon numberrange are selected.

The expression “C_(a)-C_(b) alkylsulfinyl” herein means an alkyl-S(O)—group in which the alkyl is a previously mentioned alkyl groupcontaining from a to b carbon atoms, such as methylsulfinyl,ethylsulfinyl, n-propylsulfinyl, i-propylsulfinyl, n-butylsulfinyl,i-butylsulfinyl, s-butylsulfinyl or tert-butylsulfinyl, and those withinthe designated carbon number range are selected.

The expression “halo (C_(a)-C_(b)) alkylsulfinyl” herein means ahaloalkyl-S(O)— group in which the haloalkyl is a previously mentionedhaloalkyl group containing from a to b carbon atoms, such asdifluoromethylsulfinyl, trifluoromethylsulfinyl,chlorodifluoromethylsulfinyl, bromodifluoromethylsulfinyl,2,2,2-trifluoroethylsulfinyl,1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethylsulfinyl ornonafluorobutylsulfinyl, and those within the designated carbon numberrange are selected.

The expression “C_(a)-C_(b) alkylsulfonyl” herein means an alkyl-SO₂—group in which the alkyl is a previously mentioned alkyl groupcontaining from a to b carbon atoms, such as methylsulfonyl,ethylsulfonyl, n-propylsulfonyl, i-propylsulfonyl, n-butylsulfonyl,i-butylsulfonyl, s-butylsulfonyl or tert-butylsulfonyl, and those withinthe designated carbon number range are selected.

The expression “halo (C_(a)-C_(b)) alkylsulfonyl” herein means ahaloalkyl-SO₂— group in which the haloalkyl is a previously mentionedhaloalkyl group containing from a to b carbon atoms, such asdifluoromethylsulfonyl, trifluoromethylsulfonyl,chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl,2,2,2-trifluoroethylsulfonyl, 1,1,2,2-tetrafluoroethylsulfonyl or2-chloro-1,1,2-trifluoroethylsulfonyl, and those within the designatedcarbon number range are selected.

The expression “C_(a)-C_(b) alkylcarbonyl” herein means an alkyl-C(O)—group in which the alkyl means a previously mentioned alkyl groupcontaining from a to b carbon atoms, such as acetyl, propionyl, butyryl,isobutyryl, valeryl, isovaleryl, 2-methylbutanoyl, pivaloyl, hexanoyl orheptanoyl, and those within the designated carbon number range areselected.

The expression “halo (C_(a)-C_(b)) alkylcarbonyl” herein means ahaloalkyl-C(O)— group in which the haloalkyl means a previouslymentioned haloalkyl group containing from a to b carbon atoms, such asfluoroacetyl, chloroacetyl, difluoroacetyl, dichloroacetyl,trifluoroacetyl, chlorodifluoroacetyl, bromodifluoroacetyl,trichloroacetyl, pentafluoropropionyl, heptafluorobutanoyl or3-chloro-2,2-dimethylpropanoyl, and those within the designated carbonnumber range are selected.

The expression “C_(a)-C_(b) alkoxycarbonyl” herein means analkyl-O—C(O)— group in which the alkyl means a previously mentionedalkyl group containing from a to b carbon atoms, such asmethoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl,i-propyloxycarbonyl, n-butoxycarbonyl, i-butoxycarbonyl,s-butoxycarbonyl, tert-butoxycarbonyl or 2-ethythexyloxycarbonyl, andthose within the designated carbon number range are selected.

The expression “halo (C_(a)-C_(b)) alkoxycarbonyl” herein means ahaloalkyl-O—C(O)— group in which the haloalkyl means a previouslymentioned haloalkyl group containing from a to b carbon atoms, such aschloromethoxycarbonyl, 2-chloroethoxycarbonyl,2,2-difluoroethoxycarbonyl, 2,2,2-trifluoroethoxycarbonyl or2,2,2-trichloroethoxycarbonyl, and those within the designated carbonnumber range are selected.

The expression such as “(C_(a)-C_(b)) cycloalkyl optionally substitutedwith Y^(a)” means a previously mentioned cycloalkyl group having from ato b carbon atoms in which hydrogen atom(s) on carbon atom(s) areoptionally substituted with optional Y^(a), and those within thedesignated carbon number range are selected. When there are two or moreY^(a)s on (C_(a)-C_(b)) cycloalkyl, each Y^(a) may be identical with ordifferent from one another.

Now, processes for producing the compounds of the present inventionrepresented by the above formula (1) will be described below. Thecompounds of the present invention may be produced, for example, by thefollowing Processes 1 to 9.

[Process 1]

Among the compounds of the present invention represented by the formula(1), a compound (1-a) wherein n is an integer of 1 or 2 may be produced,for example, by reacting a compound (1-b) of the present inventionwherein n is an integer of 0 and an oxidizing agent.

wherein D substituted with —S(O)_(n)R¹, Q and R¹ are as defined above,and n′ is an integer of 1 or 2.

The compound (1-a) may be produced by reacting the compound (1-b) and anoxidizing agent in a solvent or without solvent and as the caserequires, in the presence of a catalyst.

In a case where a solvent is used, the solvent may be any solvent whichis inert to the reaction and may, for example, be water, a lower alcoholsuch as methanol or ethanol, an ether such as diethyl ether,tetrahydrofuran, 1,4-dioxane or 1,2-dimethoxyethane, an aromatichydrocarbon such as benzene, chlorobenzene, bromobenzene, xylene ortoluene, an aliphatic hydrocarbon such as pentane, hexane orcyclohexane, a halogenated hydrocarbon such as dichloromethane,chloroform or 1,2-dichloroethane, a nitrile such as acetonitrile orpropionitrile, an amide such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylpyrrolidone orN,N′-dimethylimidazolidinone, a sulfoxide such as dimethylsulfoxide, alower fatty acid such as acetic acid, or a mixture thereof. Hereinafterthe above-exemplified solvents and mixtures thereof will generically bereferred to as “solvent A”.

The oxidizing agent may, for example, be a peracid such asm-chloroperbenzoic acid or peracetic acid, hydrogen peroxide or OXONE(tradename, manufactured by E. I. du Pont, potassium peroxymonosulfatecontent). The amount of the oxidizing agent used is from 0.1 to 100equivalent amount, preferably from 1 to 20 equivalent amount per 1equivalent amount of the compound (1-b).

The reaction may be carried out in the presence of a catalyst. Thecatalyst may, for example, be sodium tungstate. The amount of thecatalyst used is from 0.005 to 20 equivalent amount, preferably from 0.1to 5 equivalent amount per 1 equivalent amount of the compound (1-b).

The reaction temperature may be set at an optional temperature of from−80° C. to the refluxing temperature of the reaction mixture, and ispreferably within a range of from 0° C. to the refluxing temperature ofthe reaction mixture.

The reaction time varies depending upon the concentration of thereaction substrate and the reaction temperature, and is optionally setusually within a range of from 5 minutes to 100 hours, and is preferablyfrom 1 to 48 hours.

According to this Process, a compound (1-1-a) may be produced from acompound (1-1-b), and a compound (1-2-a) may be produced from a compound(1-2-b).

wherein R¹, R², R³, A¹, A⁴, A⁵, Y1, Y2, Y3, Y4 and n′ are as definedabove. [Process 2]

The compound (1-1-b) may be produced, for example, by reacting acompound (3-1) and a compound (10).

wherein R¹, R², R³, A¹, A⁴, A⁵, Y1, Y2, Y3 and Y4 are as defined above.

The compound (1-1-b) may be produced by reacting the compound (3-1) andthe compound (10) in the presence of a halogenating agent in a solventor without solvent.

In a case where a solvent is used, the solvent may be any solvent whichis inert to the reaction and may, for example, be the above-mentioned“solvent A”.

The halogenating agent may, for example, be chlorine, bromine, iodine,N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide,1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin or1,3-diiodo-5,5-dimethylhydantoin. The amount of the halogenating agentis from 0.5 to 50 equivalent amount, preferably from 1 to 20 equivalentamount per 1 equivalent amount of the compound (3-1).

The reaction temperature may be set at an optional temperature of from−80° C. to the refluxing temperature of the reaction mixture, and ispreferably within a range of from 0° C. to the refluxing temperature ofthe reaction mixture.

The reaction time varies depending upon the concentration of thereaction substrate and the reaction temperature, and is optionally setusually within a range of from 5 minutes to 100 hours, and is preferablyfrom 1 to 48 hours.

With respect to the amount of the substrate used, the amount of thecompound (10) may be from 0.5 to 50 equivalent amount, preferably from 1to 20 equivalent amount per 1 equivalent amount of the compound (3-1).

Some of the compounds (10) are known compounds, and some of them arecommercially available.

[Process 3]

Among the compounds (1) of the present invention, the compound (1-b) maybe produced, for example, by reacting a compound (2) and a compound(11).

wherein D substituted with —S(O)_(n)R¹, Q and R¹ are as defined above,L¹ is a chlorine atom, a bromine atom or an iodine atom, and W¹ is ahydrogen atom, a sodium atom or a potassium atom.

The compound (1-b) may be produced by reacting the compound (2) and thecompound (11) in a solvent or without solvent and as the case requires,in a presence of a base, a palladium catalyst and a ligand.

In a case where a solvent is used, the solvent may be any solvent whichis inert to the reaction and may, for example, be the above-mentioned“solvent A”.

The reaction may be carried out in the presence of a base. The base may,for example, be an organic base such as pyridine, 2,6-lutidine,triethylamine, diisopropylethylamine, tributylamine,4-(dimethylamino)pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO),1,8-diazabicyclo[5.4.0]-7-undecene (DBU) or1,5-diazabicyclo[4.3.0]-5-nonene (DBN), or an inorganic base such assodium hydroxide, potassium hydroxide, sodium hydride, sodium hydrogencarbonate, potassium carbonate or cesium carbonate. The amount of thebase used is from 0.1 to 100 equivalent amount, preferably from 1 to 20equivalent amount per 1 equivalent amount of the compound (2).

The reaction may be carried out in the presence of a palladium catalyst.The palladium catalyst may, for example, be palladium-carbon,palladium(II) chloride, palladium(II) acetate,bis(triphenylphosphine)palladium(II) dichloride,tetrakis(triphenylphosphine)palladium(0),bis(dibenzylideneacetone)palladium(0) ortris(dibenzylideneacetone)dipalladium(0). The amount of the palladiumcatalyst used may be from 0.005 to 20 equivalent amount, preferably from0.01 to 5 equivalent amount per 1 equivalent amount of the compound (2).

The reaction may be carried out in the presence of a ligand. The ligandmay, for example, be 4,5′-bis(diphenylphosphino)-9,9′-dimethylxantheneor 1,10-phenanthroline. The amount of the ligand used may be from 0.005to 20 equivalent amount, preferably from 0.01 to 5 equivalent amount per1 equivalent amount of the compound (2).

The reaction temperature may be set at an optional temperature of from−80° C. to the refluxing temperature of the reaction mixture, and ispreferably within a range of from 0° C. to the refluxing temperature ofthe reaction mixture.

The reaction time varies depending upon the concentration of thereaction substrate and the reaction temperature, and is optionally setusually within a range of from 5 minutes to 100 hours, and is preferablyfrom 1 to 48 hours.

With respect to the amount of the substrate, the amount of the compound(11) may be from 0.5 to 50 equivalent amount, preferably from 1 to 20equivalent amount per 1 equivalent amount of the compound (2).

Some of the compounds (11) are known compounds, and some of them arecommercially available.

According to this Process, for example, the compound (1-1-b) may beproduced from a compound (2-1), and the compound (1-2-b) may be producedfrom a compound (2-2).

wherein R¹, R², R³, A¹, A⁴, A⁵, Y1, Y2, Y3, Y4, L¹ and W¹ are as definedabove.

[Process 4]

Among the compounds (1) of the present invention, a compound (1-d) and acompound (1-e) may be produced, for example, by reacting a compound(1-c) wherein one or more of Y1, Y2, Y3 and Y4 is a halogen atom amongthe compounds (1) of the present invention and a compound (12-1) or acompound (12-2).

wherein D substituted with —S(O)_(n)R¹, Q, R¹, G1, G2 and n are asdefined above, X¹ is a halogen atom, m is an integer of 1, 2, 3 or 4, W²is Sn(R)₃, B(OR^(b))₂ or the like, R^(a) is C₁-C₆ alkyl, and R^(b) is ahydrogen atom or C₁-C₆ alkyl.

The compound (1-d) may be produced by reacting the compound (1-c) andthe compound (12-1), and the compound (1-e) may be produced by reactingthe compound (1-c) and the compound (12-2), respectively in a solvent orwithout solvent in the presence of a catalyst, a ligand and a base.

In a case where a solvent is used, the solvent may be any solvent whichis inert to the reaction and may, for example, be the above-mentioned“solvent A”.

The catalyst may, for example, be palladium-carbon, palladium(II)chloride, palladium(II) acetate, bis(triphenylphosphine)palladium(II)dichloride, tetrakis(triphenylphosphine)palladium(0),bis(dibenzylideneacetone)palladium(0),tris(dibenzylideneacetone)dipalladium(0), or copper(I) iodide. Theamount of the catalyst used may be from 0.005 to 20 equivalent amount,preferably from 0.01 to 5 equivalent amount per 1 equivalent amount ofthe compound (1-c).

The ligand may, for example, be4,5′-bis(diphenylphosphino)-9,9′-dimethylxanthene, 1,10-phenanthroline,1,2-diaminoethane, N,N′-dimethylethylenediamine orN,N′-dimethylcyclohexane-1,2-diamine. The amount of the ligand used maybe from 0.005 to 20 equivalent amount, preferably from 0.01 to 5equivalent amount per 1 equivalent amount of the compound (1-c).

The base may, for example, be an organic base such as pyridine,2,6-lutidine, triethylamine, diisopropylethylamine, tributylamine,4-(dimethylamino)pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO),1,8-diazabicyclo[5.4.0]-7-undecene (DBU) or1,5-diazabicyclo[4.3.0]-5-nonene (DBN), or an inorganic base such assodium hydroxide, potassium hydroxide, sodium hydride, sodium hydrogencarbonate, potassium carbonate or cesium carbonate. The amount of thebase used is from 0.1 to 100 equivalent amount, preferably from 1 to 20equivalent amount per 1 equivalent amount of the compound (1-c).

The reaction temperature may be set at an optional temperature of from−80° C. to the refluxing temperature of the reaction mixture, and ispreferably within a range of from 0° C. to the refluxing temperature ofthe reaction mixture.

The reaction time varies depending upon the concentration of thereaction substrate and the reaction temperature, and is optionally setusually within a range of from 5 minutes to 100 hours, and is preferablyfrom 1 to 48 hours.

With respect to the amount of the substrate, the amount of the compound(12-1) and the compound (12-2) may be used from 0.5 to 50 equivalentamount, preferably from 1 to 20 equivalent amount per 1 equivalentamount of the compound (1-c).

Some of the compounds (12-1) and the compounds (12-2) are knowncompounds, and some of them are commercially available.

According to this Process, for example, a compound (1-1-e) may beproduced from a compound (1-1-c).

wherein R¹, R², R³, A¹, A⁴, A⁵, G2, X¹, n and m are as defined above.

[Process 5]

Among the compounds (1) of the present invention, the compound (1-3) maybe produced, for example, by reacting a compound (13) and a compound(5-1) in accordance with Synthetic Example 11 disclosed inWO2016/129684.

wherein R¹, R², R³, R⁶, A⁴, A⁵, Y1, Y2, Y3, Y4, X¹ and n are as definedabove.

Some of the compounds (13) are known compounds, and some of them arecommercially available. The rest of them may be prepared in accordancewith known methods, for example, in accordance with the reactionconditions disclosed in WO2016/129684 or the like.

[Process 6]

Among the compounds (1) of the present invention, a compound (1-4) maybe produced, for example, by reacting a compound (14) and a compound(5-1) in accordance with Synthetic Example 14 disclosed inWO2016/129684.

wherein R¹, R⁶, R⁷, A⁸, Y1, Y2, Y3, Y4, X¹ and n are as defined above.

Some of the compounds (14) are known compounds, and some of them arecommercially available. The rest of them may be prepared in accordancewith known methods, for example, in accordance with the reactionconditions disclosed in Journal of Fluorine Chemistry, 2012, vol. 133,p. 115, or the like.

[Process 7]

Among the compounds (1) of the present invention, a compound (1-5) maybe produced, for example, by reaction from a compound (5-2) inaccordance with Synthetic Example 17 disclosed in WO2016/129684.

wherein R¹, R², R³, R⁶, A⁴, A⁵, Y1, Y2, Y3, Y4 and n are as definedabove.

Some of the compounds (15) are known compounds, and some of them arecommercially available. The rest of them may be prepared in accordancewith known methods, for example, in accordance with Process disclosed inWO2016/129684 or the like.

[Process 8]

Among the compounds (1) of the present invention, a compound (1-6) maybe produced, for example, by reacting a compound (5-3) and a compound(16).

wherein R¹, R², R³, A⁴, A⁵, Y1, Y2, Y3, Y4 and n are as defined above,and Ar¹ is a non-substituted or substituted benzene such as a phenylgroup, a p-tolyl group or a 2,4,6-trimethylphenyl group.

The compound (1-6) may be produced by reacting the compound (5-3) andthe compound (16) in a solvent or without solvent in the presence of adehydration condensation agent, and as the case requires, in thepresence of a base.

In a case where a solvent is used, the solvent may be any solvent whichis inert to the reaction and may, for example, be the above-mentioned“solvent A”.

The dehydration condensation agent may, for example, be1H-benzotriazol-1-yloxytris(dimethylamino)phosphoniumhexafluorophosphate, N,N′-dicyclohexylcarbodiimide or1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride. The amountof the dehydration condensation agent used is from 0.1 to 100 equivalentamount, preferably from 1 to 20 equivalent amount per 1 equivalentamount of the compound (16).

The reaction may be carried out in the presence of a base. The base may,for example, be an organic base such as pyridine, triethylamine or4-(dimethylamino)pyridine, or an inorganic base such as sodiumhydroxide, potassium carbonate or cesium carbonate. The amount of thebase used is from 0.1 to 100 equivalent amount, preferably from 1 to 20equivalent amount per 1 equivalent amount of the compound (16).

The reaction time varies depending upon the concentration of thereaction substrate and the reaction temperature, and is optionally setusually within a range of from 5 minutes to 100 hours, and is preferablyfrom 1 to 48 hours.

With respect to the amount of the substrate, the amount of the compound(5-3) may be from 0.5 to 50 equivalent amount, preferably from 1 to 20equivalent amount per 1 equivalent amount of the compound (16).

Some of the compounds (16) are known compounds, and some of them arecommercially available. The rest of them may be prepared, for example,in accordance with the method disclosed in WO2009/157423, WO2014/133046,WO2015/000715, or the like.

[Process 9]

Among the compounds (1) of the present invention, a compound (1-7) maybe produced, for example, by reacting a compound (17) and a compound(5-4).

wherein R¹, R², R³, A⁴, Y1, Y2, Y3, Y4 and n are as defined above, andX² is a chlorine atom. PF₆ or ClO₄.

The compound (1-7) may be produced by reacting the compound (17) and thecompound (5-4) in a solvent or without solvent and as the case requires,in the presence of a base.

In a case where a solvent is used, the solvent may be any solvent whichis inert to the reaction and may, for example, be the above-mentioned“solvent A”.

The reaction may be carried out in the presence of a base. The base may,for example, be an organic base such as pyridine, triethylamine or4-(dimethylamino)pyridine, an inorganic base such as sodium hydroxide,sodium hydride, potassium carbonate or cesium carbonate, or an alkalimetal alkoxide such as sodium methoxide or potassium tert-butoxide. Theamount of the base used is from 0.1 to 100 equivalent amount, preferablyfrom 1 to 20 equivalent amount per 1 equivalent amount of the compound(17).

The reaction temperature may be set at an optional temperature of from−80° C. to the refluxing temperature of the reaction mixture, and ispreferably within a range of from 0° C. to the refluxing temperature ofthe reaction mixture.

The reaction time varies depending upon the concentration of thereaction substrate and the reaction temperature, and is optionally setusually within a range of from 5 minutes to 100 hours, and is preferablyfrom 1 to 48 hours.

With respect to the amount of the substrate, the amount of the compound(5-4) may be from 0.5 to 50 equivalent amount, preferably from 1 to 20equivalent amount per 1 equivalent amount of the compound (17).

Some of the compounds (17) are known compounds, and some of them arecommercially available.

The compound (3-1) used in Process 2 and the compound (2-1) used inProcess 3 may be prepared, for example, in accordance with the followingReaction Schemes.

wherein R², R³, A¹, A⁴, A⁵, Y1, Y2, Y3, Y4 and L¹ are as defined above.

Step 1: A compound (4-2) may be produced, for example, by reacting acompound (18) and a compound (6-1) in a solvent or without solvent inthe presence of a dehydration condensation agent and as the caserequires, in the presence of a base and as the case requires, in thepresence of a catalyst.

In a case where a solvent is used, the solvent may be any solvent whichis inert to the reaction and may, for example, be the above-mentioned“solvent A”.

The dehydration condensation agent may, for example, be1H-benzotriazol-1-yloxytris(dimethylamino)phosphoniumhexafluorophosphate, N,N′-dicyclohexylcarbodiimide,1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride,2-chloro-1-methylpyridinium iodide orO-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluroniumhexafluorophosphate. The amount of the dehydration condensation agentused is from 0.1 to 100 equivalent amount, preferably from 1 to 20equivalent amount per 1 equivalent amount of the compound (18).

The reaction may be carried out in the presence of a base. The base tobe used may, for example, be an organic base such as pyridine,2,6-lutidine, triethylamine, diisopropylethylamine, tributylamine,4-(dimethylamino)pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO),1,8-diazabicyclo[5.4.0]-7-undecene (DBU) or1,5-diazabicyclo[4.3.0]-5-nonene (DBN), or an inorganic base such assodium hydroxide, potassium hydroxide, sodium hydride, sodium hydrogencarbonate, potassium carbonate or cesium carbonate. The amount of thebase used is from 0.1 to 100 equivalent amount, preferably from 1 to 20equivalent amount per 1 equivalent amount of the compound (18).

The reaction may be carried out in the presence of a catalyst. Thecatalyst may, for example, be 1-hydroxybenzotriazole or4-(dimethylamino)pyridine. The amount of the catalyst used is from 0.005to 20 equivalent amount, preferably from 0.1 to 5 equivalent amount per1 equivalent amount of the compound (18).

The reaction time varies depending upon the concentration of thereaction substrate and the reaction temperature, and is optionally setusually within a range of from 5 minutes to 100 hours, and is preferablyfrom 1 to 48 hours.

With respect to the amount of the substrate, the amount of the compound(6-1) may be from 0.5 to 50 equivalent amount, preferably from 1 to 20equivalent amount per 1 equivalent amount of the compound (18).

Some of the compounds (18) are known compounds, and some of them arecommercially available.

Some of the compounds (6-1) are known compounds, and some of them arecommercially available. The rest of them may be prepared, for example,in accordance with the reaction conditions disclosed in WO2009/095253,WO2011/015343, or the like.

Step 2: The compound (3-1) may be produced, for example, by subjectingthe compound (4-2) to reaction in a solvent or without solvent and asthe case requires, in the presence of an acid or a dehydrationcondensation agent.

In a case where a solvent is used, the solvent may be any solvent whichis inert to the reaction and may, for example, be a lower alcohol suchas methanol or ethanol, an ether such as diethyl ether, tetrahydrofuran,1,4-dioxane or 1,2-dimethoxyethane, an aromatic hydrocarbon such asbenzene, chlorobenzene, bromobenzene, xylene or toluene, an aliphatichydrocarbon such as pentane, hexane or cyclohexane, a halogenatedhydrocarbon such as dichloromethane, chloroform or 1,2-dichloroethane, anitrile such as acetonitrile or propionitrile, an amide such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone orN,N′-dimethylimidazolidinone, a sulfoxide such as dimethylsulfoxide, anitrogen-containing aromatic compound such as pyridine, or a mixturethereof. Hereinafter the above-exemplified solvents and mixtures thereofwill generically be referred to as “solvent B”.

The reaction may be carried out in the presence of an acid. The acidmay, for example, be p-toluenesulfonic acid, polyphosphoric acid, aceticacid or propionic acid. The amount of the acid used is from 0.1 to 1,000equivalent amount, preferably from 1 to 500 equivalent amount per 1equivalent amount of the compound (4-2).

The reaction may be carried out in the presence of a dehydrationcondensation agent. The dehydration condensation agent may, for example,be phosphorus oxychloride or acetic anhydride. The amount of thedehydration condensation agent used is from 0.5 to 50 equivalent amount,preferably from 1 to 20 equivalent amount per 1 equivalent amount of thecompound (4-2).

The reaction temperature may be set at an optional temperature of from−80° C. to the refluxing temperature of the reaction mixture, and ispreferably within a range of from 0° C. to the refluxing temperature ofthe reaction mixture.

The reaction time varies depending upon the concentration of thereaction substrate and the reaction temperature, and is optionally setusually within a range of from 5 minutes to 100 hours, and is preferablyfrom 1 to 48 hours.

Step 3: The compound (2-1) may be produced, for example, by reacting thecompound (3-1) and a halogenating agent in a solvent or without solvent.

In a case where a solvent is used, the solvent may be any solvent whichis inert to the reaction and may, for example, be the above-mentioned“solvent A”.

The halogenating agent may, for example, be chlorine, bromine, iodine,N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide,1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin or1,3-diiodo-5,5-dimethylhydantoin. The amount of the halogenating agentused is from 0.5 to 50 equivalent amount, preferably from 1 to 20equivalent amount per 1 equivalent amount of the compound (3-1).

The reaction temperature may be set at an optional temperature of from−80° C. to the refluxing temperature of the reaction mixture, and ispreferably within a range of from 0° C. to the refluxing temperature ofthe reaction mixture.

The reaction time varies depending upon the concentration of thereaction substrate and the reaction temperature, and is optionally setusually within a range of from 5 minutes to 100 hours, and is preferablyfrom 1 to 48 hours.

A compound (2-a) including the compound (2-2) used in Process 3 may beproduced, for example, in accordance with the following Reaction Scheme.

wherein Q, Y1, Y2, Y3, Y4 and L¹ are as defined above.

Step 1: A compound (4-a) may be produced, for example, by reacting acompound (5-a) and a compound (19) in a solvent or without solvent andas the case requires, in the presence of an acid.

In a case where a solvent is used, the solvent may be any solvent whichis inert to the reaction and may, for example, be the above-mentioned“solvent B”.

The reaction may be carried out in the presence of an acid. The acidmay, for example, be p-toluenesulfonic acid, acetic acid or formic acid.The amount of the acid used is from 0.1 to 1,000 equivalent amount,preferably from 1 to 20 equivalent amount per 1 equivalent amount of thecompound (5-a).

The reaction temperature may be set at an optional temperature of from−80° C. to the refluxing temperature of the reaction mixture, and ispreferably within a range of from 0° C. to the refluxing temperature ofthe reaction mixture.

The reaction time varies depending upon the concentration of thereaction substrate and the reaction temperature, and is optionally setusually within a range of from 5 minutes to 100 hours, and is preferablyfrom 1 to 48 hours.

With respect to the amount of the substrate, the amount of the compound(19) may be from 0.5 to 50 equivalent amount, preferably from 1 to 20equivalent amount per 1 equivalent amount of the compound (5-a).

Some of the compounds (5-a) are known compounds, and some of them arecommercially available. The rest of them may be prepared, for example,in accordance with the method disclosed in WO2002/081478, WO2004/098494,WO2009/136663, European Journal of Medicinal Chemistry, 2014, vol. 87,p. 386, WO2011/075615, WO2011/090127, WO2015/114452, or the like.

Some of the compounds (19) are known compounds, and some of them arecommercially available.

Step 2: A compound (3-a) may be produced, for example, by reacting thecompound (4-a) and a reducing agent in a solvent or without solvent.

In a case where a solvent is used, the solvent may be any solvent whichis inert to the reaction and may, for example, be the above-mentioned“solvent B”.

The reducing agent may, for example, be trimethylphosphine,triethylphosphine, tributylphosphine or triethylphosphite. The amount ofthe reducing agent used is from 0.5 to 50 equivalent amount, preferablyfrom 1 to 20 equivalent amount per 1 equivalent amount of the compound(4-a).

The reaction temperature may be set at an optional temperature of from−80° C. to the refluxing temperature of the reaction mixture, and ispreferably within a range of from 0° C. to the refluxing temperature ofthe reaction mixture.

The reaction time varies depending upon the concentration of thereaction substrate and the reaction temperature, and is optionally setusually within a range of from 5 minutes to 100 hours, and is preferablyfrom 1 to 48 hours.

Step 3: The compound (2-a) may be produced, for example, by reacting thecompound (3-a) and a halogenating agent in a solvent or without solvent.

In a case where a solvent is used, the solvent used may be any solventwhich is inert to the reaction and may, for example, the above-mentioned“solvent A”.

The halogenating agent may, for example, be chlorine, bromine, iodine,N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide,1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin or1,3-diiodo-5,5-dimethylhydantoin. The amount of the halogenating agentused is from 0.5 to 50 equivalent amount, preferably from 1 to 20equivalent amount per 1 equivalent amount of the compound (3-a).

The reaction temperature may be set at an optional temperature of from−80° C. to the refluxing temperature of the reaction mixture, and ispreferably within a range of from 0° C. to the refluxing temperature ofthe reaction mixture.

The reaction time varies depending upon the concentration of thereaction substrate and the reaction temperature, and is optionally setusually within a range of from 5 minutes to 100 hours, and is preferablyfrom 1 to 48 hours.

According to process represented by Reaction Scheme 2, for example, thecompound (2-2) to be used for Process 3 may be produced.

wherein R², R³, A¹, A⁴, A⁵, Y1, Y2, Y3, Y4 and L¹ are as defined above.

The compound (2-2) used in Process 3 may be produced, for example, inaccordance with the following Reaction Scheme.

wherein R², R³, A¹, A⁴, A⁵, Y1, Y2, Y3, Y4 and L¹ are as defined above.

Step 1: A compound (5-5) is subjected to a dehydration condensationreaction with a compound (20) in accordance with the method disclosed instep 1 of Reaction Scheme 1 to produce a compound (4-4). Some of thecompounds (20) are known compounds, and some of them are commerciallyavailable.

Step 2: The compound (4-4) is reacted with a halogenating agent inaccordance with a known method, for example, in accordance with themethod disclosed in WO2011/153588 or the like, to produce the compound(2-2).

The compound (5-5) used in Reaction Schemes 3 and 4 may be produced, forexample, in accordance with the following Reaction Scheme.

wherein R², R³, A¹, A⁴ and A⁵ are as defined above.

The compound (5-5) may be produced, for example, by reacting thecompound (18) and cyanogen bromide in a solvent or without solvent.

In a case where a solvent is used, the solvent used may be any solventwhich is inert to the reaction and may, for example, the above-mentioned“solvent B”.

The reaction temperature may be set at an optional temperature of from−80° C. to the refluxing temperature of the reaction mixture, and ispreferably within a range of from 0° C. to the refluxing temperature ofthe reaction mixture.

The reaction time varies depending upon the concentration of thereaction substrate and the reaction temperature, and is optionally setusually within a range of from 5 minutes to 100 hours, and is preferablyfrom 1 to 48 hours.

With respect to the amount of the substrate, the amount of cyanogenbromide may be from 0.5 to 50 equivalent amount, preferably from 1 to 20equivalent amount per 1 equivalent amount of the compound (18).

The compound (5-1) to be used in Process 5 and Process 6 may beproduced, for example, from a compound (5-3-b) as a starting material inaccordance with Reaction Scheme 1 disclosed in WO2016/129684, inaccordance with the following Reaction Scheme. A compound (5-1-a) is acompound (5-1) wherein n is an integer of 1 or 2, and a compound (5-1-b)is a compound (5-1) wherein n is an integer of 0.

wherein R¹, R⁶, Y1, Y2, Y3, Y4, X¹ and n′ are as defined above, X³ is achlorine atom, a bromine atom or an iodine atom, and n′ is an integer of1 or 2.

The compound (5-2) used in Process 7 may be produced, for example, inaccordance with the following Reaction Scheme.

wherein R¹, Y1, Y2, Y3, Y4, n and R^(a) are as defined above.

Step 1: The compound (5-3) is reacted with diphenylphosphoryl azide(DPPA) and a compound (22) in accordance with a known method disclosedin literature, for example, in accordance with the method disclosed inWO2012/174312, WO2003/018021 or the like, to produce a compound (7).Some of the compounds (22) are known compounds, and some of them arecommercially available.

Step 2: The compound (7) is reacted with an acid in accordance with aknown method, for example, in accordance with the method disclosed inWO2012/174312, WO2003/018021 or the like, to produce the compound (5-2).

The compound (5-3) used in Process 8 and Reaction Scheme 7 may beproduced, for example, from a compound (8-3) as a starting material inaccordance with Reaction Scheme 1 disclosed in WO2016/129684 inaccordance with the following Reaction Scheme. A compound (5-3-a) is acompound (5-3) wherein n is an integer of 1 or 2, and the compound(5-3-b) is a compound (5-3) wherein n is an integer of 0.

wherein R¹, Y2, Y2, Y3, Y4, L¹, R^(a) and n′ are as defined above.

Some of the compounds (8-3) are known compounds, and some of them arecommercially available. The rest of them may be prepared, in accordancewith a known method, for example, in accordance with the reactionconditions disclosed in WO2011/050284 or the like.

The compound (5-4) used in Process 9 may be produced, for example, inaccordance with the following Reaction Scheme.

wherein R¹, Y1, Y2, Y3, Y4, R^(a) and n are as defined above.

Step 1: A compound (8-1) is reacted with acetonitrile in accordance witha known method, for example, in accordance with the method disclosed inOrganic Letters, 2009, vol. 11, p. 2417, to produce a compound (9). Thecompound (8-1) may be produced in accordance with Reaction Scheme 8.

Step 2: The compound (9) is reacted with hydrazine monohydrate inaccordance with a known method, for example, in accordance with themethod disclosed in WO2011/105628, Bioorganic & Medicinal ChemistryLetters, 2010, vol. 20, p. 922, or the like, to produce the compound(5-4).

In Processes 1 to 9 and Reaction Schemes 1 to 9, the reaction mixtureafter the reaction can be worked up by an ordinary procedure, forexample, by direct concentration, by dissolving the reaction mixture inan organic solvent and washing the solution with water, followed byconcentration, or by pouring the reaction mixture into ice water,followed by extraction with an organic solvent and concentration, toobtain the desired compound of the present invention. Further, ifnecessary, the desired product may be isolated or purified by anoptional purification method such as recrystallization, columnchromatography, thin layer chromatography or liquid chromatography.

As the condensed heterocyclic compounds represented by the formula (1)of the present invention, which can be produced by the above methods,compounds shown in the following Table 1 may be mentioned. However, thecompounds shown in Table 1 merely exemplify the present invention, andthe present invention is by no means restricted thereto. In Tables, J1,J2, J3, J4, J5, J6, J7, J8, J9, J10, J11, J12, J13 and J14 represent thefollowing cyclic structures.

In Table, Me represents a methyl group, and Et represents an ethylgroup.

TABLE 1

Y1 Y2 Y3 Y4 n H H H H 0 H H H H 1 H H H H 2 F H H H 0 F H H H 1 F H H H2 Cl H H H 0 Cl H H H 1 Cl H H H 2 Br H H H 0 Br H H H 1 Br H H H 2 I HH H 0 I H H H 1 I H H H 2 Me H H H 0 Me H H H 1 Me H H H 2 CF₃ H H H 0CF₃ H H H 1 CF₃ H H H 2 H F H H 0 H F H H 1 H F H H 2 H Cl H H 0 H Cl HH 1 H Cl H H 2 H Br H H 0 H Br H H 1 H Br H H 2 H I H H 0 H I H H 1 H IH H 2 H Me H H 0 H Me H H 1 H Me H H 2 H SOCF₃ H H 0 H SOCF₃ H H 1 HSOCF₃ H H 2 H SO₂CF₃ H H 0 H CF₃ H H 0 H CF₃ H H 1 H CF₃ H H 2 H CF₂CF₃H H 0 H CF₂CF₃ H H 1 H CF₂CF₃ H H 2 H CF(CF₃₎₂ H H 0 H CF(CF₃₎₂ H H 1 HCF(CF₃₎₂ H H 2 H SMe H H 0 H SMe H H 1 H SMe H H 2 H SOMe H H 0 H SOMe HH 1 H SOMe H H 2 H SO₂Me H H 0 H SO₂Me H H 1 H SO₂Me H H 2 H OMe H H 0 HOMe H H 1 H OMe H H 2 H OCF₃ H H 0 H OCF₃ H H 1 H OCF₃ H H 2 H NO₂ H H 0H NO₂ H H 1 H NO₂ H H 2 H NH₂ H H 0 H NH₂ H H 1 H NH₂ H H 2 H CN H H 0 HCN H H 1 H CN H H 2 H SCF₃ H H 0 H SCF₃ H H 1 H SCF₃ H H 2 H H SO₂Me H 0H H SO₂Me H 1 H H SO₂Me H 2 H H OMe H 0 H SO₂CF₃ H H 1 H SO₂CF₃ H H 2 HH F H 0 H H F H 1 H H F H 2 H H Cl H 0 H H Cl H 1 H H Cl H 2 H H Br H 0H H Br H 1 H H Br H 2 H H I H 0 H H I H 1 H H I H 2 H H Me H 0 H H Me H1 H H Me H 2 H H CF₃ H 0 H H CF₃ H 1 H H CF₃ H 2 H H CF₂CF₃ H 0 H HCF₂CF₃ H 1 H H CF₂CF₃ H 2 H H CF(CF₃)₂ H 0 H H CF(CF₃)₂ H 1 H H CF(CF₃)₂H 2 H H SMe H 0 H H SMe H 1 H H SMe H 2 H H SOMe H 0 H H SOMe H 1 H HSOMe H 2 H H H I 0 H H H I 1 H H H I 2 H H H Me 0 H H H Me 1 H H H Me 2H H H CF₃ 0 H H H CF₃ 1 H H OMe H 1 H H OMe H 2 H H OCF₃ H 0 H H OCF₃ H1 H H OCF₃ H 2 H H NO₂ H 0 H H NO₂ H 1 H H NO₂ H 2 H H NH₂ H 0 H H NH₂ H1 H H NH₂ H 2 H H CN H 0 H H CN H 1 H H CN H 2 H H SCF₃ H 0 H H SCF₃ H 1H H SCF₃ H 2 H H SOCF₃ H 0 H H SOCF₃ H 1 H H SOCF₃ H 2 H H SO₂CF₃ H 0 HH SO₂CF₃ H 1 H H SO₂CF₃ H 2 H H H F 0 H H H F 1 H H H F 2 H H H Cl 0 H HH Cl 1 H H H Cl 2 H H H Br 0 H H H Br 1 H H H Br 2 H J10 H H 0 H J10 H H1 H J10 H H 2 H J11 H H 0 H J11 H H 1 H J11 H H 2 H J12 H H 0 H J12 H H1 H H H CF₃ 2 H J1 H H 0 H J1 H H 1 H J1 H H 2 H J2 H H 0 H J2 H H 1 HJ2 H H 2 H J3 H H 0 H J3 H H 1 H J3 H H 2 H J4 H H 0 H J4 H H 1 H J4 H H2 H J5 H H 0 H J5 H H 1 H J5 H H 2 H J6 H H 0 H J6 H H 1 H J6 H H 2 H J7H H 0 H J7 H H 1 H J7 H H 2 H J8 H H 0 H J8 H H 1 H J8 H H 2 H J9 H H 0H J9 H H 1 H J9 H H 2 H H J8 H 0 H H J8 H 1 H H J8 H 2 H H J9 H 0 H H J9H 1 H H J9 H 2 H H J10 H 0 H H J10 H 1 H H J10 H 2 H H J11 H 0 H H J11 H1 H H J11 H 2 H J12 H H 2 H J13 H H 0 H J13 H H 1 H J13 H H 2 H J14 H H0 H J14 H H 1 H J14 H H 2 H H J1 H 0 H H J1 H 1 H H J1 H 2 H H J2 H 0 HH J2 H 1 H H J2 H 2 H H J3 H 0 H H J3 H 1 H H J3 H 2 H H J4 H 0 H H J4 H1 H H J4 H 2 H H J5 H 0 H H J5 H 1 H H J5 H 2 H H J6 H 0 H H J6 H 1 H HJ6 H 2 H H J7 H 0 H H J7 H 1 H H J7 H 2 H H H J6 0 H H H J6 1 H H H J6 2H H H J7 0 H H H J7 1 H H H J7 2 H H H J8 0 H H H J8 1 H H H J8 2 H H HJ9 0 H H H J9 1 H H H J9 2 H H J12 H 0 H H J12 H 1 H H J12 H 2 H H J13 H0 H H J13 H 1 H H J13 H 2 H H J14 H 0 H H J14 H 1 H H J14 H 2 H H H J1 0H H H J1 1 H H H J1 2 H H H J2 0 H H H J2 1 H H H J2 2 H H H J3 0 H H HJ3 1 H H H J3 2 H H H J4 0 H H H J4 1 H H H J4 2 H H H J5 0 H H H J5 1 HH H J5 2 H H H J10 0 H H H J10 1 H H H J10 2 H H H J11 0 H H H J11 1 H HH J11 2 H H H J12 0 H H H J12 1 H H H J12 2 H H H J13 0 H H H J13 1 H HH J13 2 H H H J14 0 H H H J14 1 H H H J14 2 H Br H CN 0 H Br H CN 1 H BrH CN 2 H I H CN 0 H I H CN 1 H I H CN 2 H Br H F 0 H Br H F 1 H Br H F 2

The pesticides herein mean pesticides for controlling harmful arthropodsin agricultural fields or in zootechnical/hygienic fields(internal/external parasites in or on mammals and birds as livestock andpets, and domestic or industrial hygienic insects/nuisance insects).

Further, the agricultural chemicals herein mean insecticides/acaricides,nematicides, herbicides and fungicides in agricultural fields.

The hygienic insects in this specification mean harmful invertebrateswhich cause allergic symptoms such as severe pain, swelling or itchingby biting the object animals and in some cases, cause fatal anaphylacticshock, sometimes transmit severe diseases due to blood sucking and insome cases, cause death, invertebrates which contaminate food withpathogens such as viruses, bacteria or parasites by being in contactwith the food, invertebrates which cause allergic diseases such asbronchitic asthma, rhinitis, conjunctivitis or atopic dermatitis, bytheir living bodies, dead bodies, exuviate, droppings, etc., asallergens, invertebrates which cause feeding damages on food, clothesand housing thereby to cause economic damages, invertebrates which donot cause direct damages but create discomfort by emergence/infestationin human living environment, etc. More specifically, the hygienicinsects mean ants which bite by mandibles, hornets which have apoisonous sting, mosquitos and kissing bugs which suck blood through theskin, and omnivorous termites which harm buildings such as houses.

The nuisance insects in this specification mean insects which creatediscomfort due to their appearances and cause physiological damages tohuman although they do not cause direct damages to human in the humanliving environment.

The insects, mites, crustaceans, mollusks and nematodes that thecompounds of the present invention can control specifically include thefollowing organisms, but the present invention is not restrictedthereto.

Insects of the order Lepidoptera such as Adoxophyes honmai, Adoxophyesorana faciata, Archips breviplicanus, Archips fuscocupreanus, Grapholitamolesta, Homona magnanima, Leguminivora glycinivorella, Matsumuraesesphaseoli, Pandemis heparana, Bucculatrix pyrivorella, Bucculatrixthurberiella, Lyonetia clerkella, Lyonetia prunifoliella malinella,Caloptilia theivora, Phyllonorycter ringniella, Phyllocnistis citrella,Acrolepiopsis sapporensis, Acrolepiopsis suzukiella, Plutellaxylostella, Stathmopoda masinissa, Helcystogramma triannulella,Pectinophora gossypiella, Lyctus brunnus, Carposina sasakii, Sinoxylonjaponicum, Rhizopertha dominica, Cydia pomonella, Chilo suppressalis,Cnaphalocrocis medinalis, Conogethes punctiferalis, Diaphania indica,Etiella zinckenlla, Glyphodes pyloalis, Hellula undalis, Ostriniafumacalis, Ostrinia scapulalis, Ostrinia nubilalis, Parapediasiateterrella, Parnara guttata, Pieris brassicae, Pieris rapae crucivora,Ascotis selenaria, Pseudoplusia includens, Euproctis pseudoconspersa,Artaxa subflava, Sphrageidus similis, Euproctis piperita, Lymantriadispar, Orgyia thyellina, Gastropachaorientalis, Dendrolimusspectabilis, Dendrolimus superans, Kunugia undans, Arctia cajaphaeosoma, Chionarctia nivea, Hyphantria cunea, Lemyra imparillis,Monema flavescens, Phrixolepia sericea, Parsa sinica, Parsa lepida,Adris tyrannus, Aedia leucomelas, Agrotis ipsilon, Agrotis segetum,Autographa nigrisigna, Ctenoplusia agnata, Helicoverpa armigera,Helicoverpa assulta, Helicoverpa zea, Heliothis virescens, Mamestrabrassicae, Mythimna separata, Naranga aenescens, Spodoptera eridania,Spodoptera exigua, Spodoptera frugiperda, Spodoptera littoralis,Spodoptera litura, Spodoptera depravata, Trichoplusia ni, Endopizaviteana, Manduca quinquemaculata, Manduca sexta, Clysia ambiguella,Eupoecilia ambiguella, Acronicta major, Amyelois transitella, Borbocinnara, Bupalus piniarius, Capua reticulana, Cheimatobia brumata,Diatraea saccharalis, Ecdytolopha aurantiana, Elasmopalpus lignosellus,Eldana saccharina, Epiphyas postvittana, Galleria mellonella,Hofmannophila pseudospretella, Yponomeuta padella, Leucinodes orbonalis,Lithophane antennata, Loxagrotis albicosta, Malacosoma neustria, Marucatestulalis, Platynota stultana, Rachiplusia nu, Scotia segetum,Stomopteryx subsecivella, Tecia solanivora, Thermesia gemmatalis, Tineapellionella, Tineola bisseliieila and Tuta absoluta.

Insects of the order Thysanoptera such as Frankliniella intonsa,Frankliniella ocddentalis, Heliothrips haemorrhoidalis, Scirtothripsdorsalis, Thrips palmi, Thrips tabaci and Ponticulothrips diospyrosi.

Insects of the order Heteroptera such as Dolycoris baccarum, Eurydemarugosum, Eysarcoris aeneus, Eysarcoris lewisi, Eysarcoris ventralis,Glaucias subpunctatus, Halyomorpha halys, Nezara antennata, Nezaraviridula, Piezodorus hybneri, Plautia crossota, Scotinophora lurida,Cletus punctiger, Leptocorisa chinensis, Riptortus clavatus, Rhopalusmsculatus, Cavelerius saccharivorus, Togo hemipterus, Dysdercuscingulatus, Stephanitis pyrioides, Halticus insularis, Lygus lineolaris,Stenodema sibiricum, Stenotus rubrovittatus, Trigonotvlus caelestialtum,Anasa tristis. Campylomma livida, Creontiades dilutus, Dasynus piperis,Dichelops furcatus, Diconocoris hewett, Horcias nobilellus, Leptoglossusphyllopus, Macropes excavatus, Monalonion atratum, Piesma quadrata,Sahlbergella singularis, Scaptocoris castanea, Pseudacysta persea andStephanitis nashi. corpulenta, Icerya purchasi, Phenacoccus solani,Planococcus citri, Planococcus kuraunhiae, Pseudococcus comstocki,Ceroplastes ceriferus, Ceroplastes rubens, Aonidielle aurentii,Comstockaspis perniciosa, Fiorinia theae, Pseudaonidia paeoniae,Pseudaulacaspis pentepona, Pseudaulacaspis prunicola, Unaspis euonymi,Unaspis yanonensis and Cimex lectularius.

Insects of the order Coleoptera such as Anomala cuprea, Anomalarufocuprea, Gametis jucunda, Heptophylla picea, Popillia japonica,Lepinotarsa decemlineata, Melanotus fortnumi, Melanotus tamsuyensis,Stedobium paniceum, Lasioderma serricorne, Epuraea domina, Epilachnavarivestis, Epilachna vigntioctopurictata, Tenebrio molitor, Triboliumcastaneum, Anoplophora malasiaca, Monochamus alternatus, Psacotheahilaris, Xylotrechus pyrrhoderus, Callosobruchus chinensis, Aulacophorafemoralis, Chaetocnema concinna, Diabrotica undectmpunctata, Diabroticavirgifera, Diabrotica barberi, Oulema oryzae, Phyllotreta striolata,Psylliodes angusticollis, Rhynchites heros, Cylas formicarius,Anthonomus grandis, Echinocnemus squameus, Euscepes postfasciatus,Hypera postica, Lissohoptrus oryzophilus, Otiorhynchus sulcatus,Sitophilus granarius, Sitophilus zeamais, Sphenophorus venatus vestitusand Paederus fuscipes.

Insects of the order Diptera such as Asphodylia yushimai, Stiodiplosismosellana, Bactocera cucurbitae, Bactrocera dorslis, Ceratits capitata,Hydellia griseola, Drosohila suzukii, Agromyza oryzae, Chromatoyiahoricola, Liriomyza bryonie, Liriomyza chinensis, Liriomyza sativae,Liriomyza trifolii, Delia platura, Peomya cunicularia, Rhagoletispomonella, Mayetiola destructor, Musca domestica, Somoxys calcitrans,Melophagus ovinus, Hypoderma bovis, Hypoderma liniatum, Oestrus ovis,Glossina palpailis, Glossina morsitans, Prosimulium yezoensis, Tabnaustrigonus, Telmatoscopus alipunctatus, Leptoconops nipponensis, Culexpipiens palles, Aedes aegypti, Aedes albopicutus, Aedes atrilisimilis,Aedes baisasi, Aedes bekkui, Aedes communis, Aedes daitensis, Aedesdiantaeus, Aedes dorsalis, Aedes ezoensis, Aedes excrucians, Aedesflavopictus, Aedes galloisi, Aedes hakusanensis, Aedes hatorii, Aedeshokkaidensis, Aedes impiger daisetuzanus, Aedes intrudens, Aedesiriomotensis, Aedes japonicus, Aedes kobayashii, Aedes koreicodies,Aedes lineatopennis, Aedes nipponicus, Aedes nishikawai, Aedesnokukonis, Aedes okinswanus, Aedes oreophilus, Aedes punctor, Aedesreversi, Aedes sasai, Aedes savoryi, Aedes seoulensis, Aedes sticticus,Aedes togoi, Aedes vexans nipponii, Aedes vigilax, Aedes wadai, Aedeswatasei, Aedes yamadai, Anopheles bengalensis, Anopheles enparensis,Anopheles koreicus, Anopheles lesten, Anopheles lindesayi japonicus,Anopheles minimus, Anopheles omorii, Anopheles saperoi, Anophelessineroides, Anopheles tessellatus, Anopheles yatsushiroensis, Armigeressubalbatus Culex bicomutus, Culex bitaeniorhynchus, Culex boninensis,Culex brevipalpis, Culex cinctellus, Culex fuscocephala, Culex havashii,Culex infantulus, Culex jacksoni, Culex kyotoensis, Culex mimeticus,Culex modestus inatormii, Culex nigropunctatus, Culex okinawae, Culexorientalis, Culex pallidothorax, Culex pipiens molestus, Culex pipiensquinquefasciatus, Culex pseudovishnui, Culex rubensis, Culexrubithorads, Culex niukyensis, Culex sasai, Culex sinensis, Culexsitiens, Culex tritaeniorhynchus, Culex tuberis, Culex vagans, Culexvishnui, Culex whitmorei, or Chironomus plumosus and Chironomusriparius.

Insects of the order Hymenoptera such as Apethymus kuri, Athalia rosae,Arge pagana, Neodiprion setter, Dryocosmus kuriphilus, Eciton burchelli,Eciton schmitti, Camponotus japonicus, Vespa mandarina, Myrmecia spp.,Solenopsis spp., Monomorium pharaonis, Tetramorium tsushimae, Lasiusjaponicus, Pachycondyla chinensis, Lasius fuliginosus, Formica fuscajaponica, Ochetelius glaber, Pristomyrmex pungens, Pheidole nods,Pheidole fentida, Linepithema humile and Cephalonomia gallicola.

Insects of the order Orthoptera such as Teleogryllus emma, Loxoblemmuscampestris, Gryllotalpa orientalis, Locusta migratoria, Oxya yezoensis,Schistocerca gregaria and Diestrammena apicalis.

Insects of the order Collembola such as Onychiurus folsomi, Onychiurussibiricus and Bourietiella hortensis.

Insects of the order Dictyoptera such as Periplaneta fuliginosa,Periplaneta japonica, Blattella germanica and Periplaneta australasiae.

Insects of the order Isoptera such as Coptotermes formosanus,Reticulitermes speratus, Odontotermes formosanus, Cornitermes cumulansand Microtermes obesi.

Insects of the order Siphonaptera such as Ctenoceohalidae felis,Ctenocephalides canis, Echidnophaga gallinacea, Pulex lrritans andXenopsylla cheopis.

Insects of he order Mallophage such as Menacanthus stramineus andBovicola bovis.

Insects of the order Anoplura such s Haematopinus eurysternus,Haematopinus Linognathus vituli and Solenopotes capillatus.

Insects of the order Thysanura such as Lepisma saccharina.

Insects of the order Psocoptera such as Psococerastis tokyoensis, andLongvalvus nubilus.

Insects of the order Anisoiabididae such as Gonolabis mardinalis.

Insects of the order Aransae such as Pardosa astrigera, Chiracanthiumjaponicum and Latrodectus hasseltii.

Taisonemidae mites such as Phytonemus pallidus, Polybhadotarsonemuslatus and Tarsonemus bilobatus.

Eupodidae mites such as Penthaleus erythrocephalus and Penthaleus major.

Tetranychidae mites such as Oligonychus shinkaii, Panonychus citri,Panonychus mori, Panonychus ulmi, Tetranychus kanzawai and Tetranychusurticae.

Eriophyidae mites such as Acaphylla theavagrans, Aceria tulipae, Aculopslycopersici, Acutops pelekassi, Aculus schlechtendali, Eriophyeschibaensis and Phyllocoptruta oleivora.

Acaridae mites such as Rhizoglyphus robini, Tyrophagus putrescentiae andTyrophagus similis.

Varroa mites such as Varroa jacobsoni.

Ticks such as Boophilus microplus, Rhipicephalus sanguineus,Haemaphysalis longicorns, Haemoohysalis flava, Haemaphysaliscampanulata, Ixodes ovatus, Ixodes persulcatus, Amblyomma spp. andDermacentor spp.

Mites of the suborder Mesostigmata such as red mite (Dermanyssusgallinae), tropical rat mite (Ornithonyssus bacoti) and northern fowlmite (Ornithonyssus sylviarum).

Cheyletidae mites such as Cheyletiella yasguri and Cheyletiella blakei.

Demodicidae mites such as Demodex canis and Demodex cati.

Psoroptidae mites such as Psoroptes ovis.

Sarcoptidae mites such, as Sarcoptes scabiei, Notoedres cati andKneidocoptes spp.

Crustaceans of the order Isopoda such as Armadilidim vulgare, Oniscusasellus and Porcellio scaber.

Crustaceans of the order Arguloida such as Argulus japonicus and Arguluscoregoni.

Crustaceans of the order Shphonostomatoida such as Lepeophtheirussalmonis and Salmincola spp.

Crustaceans of the order Cyclopoida such as Lernaea cyprinacea.

Centipedes of the class Chilopoda, the order Scolopendromorpha such asScolopendra subspinipes, Scolopendra japonica and Scolopendra multidens,the order Lithobiomorpha such as Bothropolys asperatus, and the orderScutigeromorpha such as Thereuonema hilgendorfi.

Millipedes of the class Diplopoda such as Oxidus gracilis, Prafontarialaminata armigera and Nedyopus tambanus.

Symphylans of the class Symphyla such as Scutigerella immculate.

Gastropods such as Pomacea canaliculata, Achatina fulica, Meghimatiumbilineatum, Limax valentiana, Limax flavus, Acusta despecta siebolidianaand Euhadra peliomphala.

Nematodes such, as Prathylenchus coffeae, Prathylenchus penetrans,Prathylenchus vulnus, Globodera rostochiensis, Heterodera glycines,Meloidogyne hapla, Meloidogyne incognita, Aphelenchoides besseyi andBursaphelenchus xylophilus.

Adult flies such as horn fly (Haematobia irritans), horse fly (Tabanusspp.), Stornoxys calcitrans, blackfly (Simulium spp.), deer fly(Chrysops spp.) louse fly (Melophagus ovinus) and tsetse fly (Glossinaspp.).

Parasitic worms such as, sheep bot fly (Oestrus ovis, Cuterebra spp.),blowfly (Phaenicia spp.), screwworm (Cochliomyia horninivorax), warblefly (Hypoderma spp.), fleeceworm and Gastrophilus.

Mosquitos such as Culex spp. Anopheles spp. and Aedes spp.

The internal, livestock, poultry or pet parasites that the compounds ofthe present invention can control specifically include the followinginternal pests, but the present so invention is not restricted thereto.

Nematodes of the genera Haemonchus, Trichostronoylus, Ostertagia,Nematodirus, Cooperia, Ascaris, Bunostomum, Oesophagostomum, Chabertia,Trichuris, Storongylus, Trichonema, Dictyoraulus, Capillaria, Heterakis,Toxocara, Ascaridia, Oxyuris, Ancylostorna, Uncinaria, Toxascaris,Parascaris, and the like.

Nematodes of the family Filariidae such as the genera Wuchereria,Brugia, Onchoceca, Dirofilaria, Loa, and the like.

Nematodes of the family Dracunculidae such as the genus Dracunculus.

Cestodes such as Dipylidium caninum, Taenia taeniaeformis, Taeniasolium, Taenia saginata Hymenolepis diminuta, Moniezia benedeni,Diphyllobothrium latum, Diphyllobothrium erinacei, Echinococcusgranulosus and Echinococcus multilocularis.

Trematodes such as Fasciola hepatica, F. gigantica, Paragonimuswestermanii, Fasciolopsic bruski, Eurytrema pancreaticum, E.coelomaticum, Clonorchis sinensis, Schistosoma japonicum, Schistosomahaematobium and Schistosoma mansoni.

Eimeria spp. such as Eimeria tenella, Eimeria acervulina, Eimeriabrunetti, Eimeria maxima, Eimeria necatrix, Eimeria bovis and Eimeriaovinoidalis.

Trypanosomsa cruzi, Leishmania spp., Plasmodium spp., Babesis spp.,Trichomonadidae spp., Histomanas spp., Giardia spp., Toxoplasma spp.Entamoeba histolytica and Theileria spp.

The compounds of the present invention are effective against pests thathave acquired resistance to conventional insecticides such as organicphosphorus compounds, carbamate compounds or pyrethroid compounds.

That is, the compounds of the present invention can effectively controlpests such as insects of the order Collembola, the order Dictyoptera,the order Orthoptera, the order Isoptera, the order Thysanoptera, theorder Hemiptera, the order Lepidoptera, the order Coleoptera, the orderHymenoptera, the order Diptera, the order Aphaniptera, the orderAnoplura, crustaceans of the order Arguloida, the orderShphonostomatoida, of the order Cyclopoida, Acari, gastropods andnematodes at low doses.

On the other hand, the compounds of the present invention have a quiteadvantageous feature that they are almost harmless to mammals, fishes,crustaceans and beneficial insects (useful insects such as honey beesand bumblebees and natural enemies such as aphelinid wasps, aphidiidwasps, tachina flies, minute pirates bug, phytoseiid mites etc.).

The compounds of the present invention may be used in any dosage formsuch as a soluble concentrate, an emulsifiable concentrate, a wettablepowder, a water soluble powder, a water dispersible granule, a watersoluble granule, a suspension concentrate, a concentrated emulsion, asuspoemulsion, a microemulsion, a dustable powder, a granule, a tabletor an emulsifiable gel usually after mixed with an appropriate solidcarrier or liquid carrier, and if necessary, with a surfactant, apenetrant, a spreader, a thickener, an anti-freezing agent, a binder, ananti-caking agent, a disintegrant, an antifoaming agent, a preservative,a stabilizer or the like. A formulation in an arbitrary dosage form maybe sealed in water-soluble packaging such as a water-soluble capsule ora water-soluble film, for labor saving or improved safety.

As solid carriers, natural minerals such as quartz, calcite, meerschaum,dolomite, chalk, kaolinite, pyrophyllite, sericite, halloysite,methahalloysite, kibushi clay, gairome clay, pottery stone, zeeklite,allophane, Shirasu, mica, talc, bentonite, activated clay, acid day,pumice, attapulgite, zeolite and diatomaceous earth; calcined naturalminerals such as calcined clay, pearlite, Shirasu-balloons, vermiculite,attapulgus clay and calcined diatomaceous earth; inorganic salts such asmagnesium carbonate, calcium carbonate, sodium carbonate, sodiumhydrogen carbonate, ammonium sulfate, sodium sulfate, magnesium sulfate,diammonium hydrogen phosphate, ammonium dihydrogen phosphate andpotassium chloride, saccharides such as glucose, fructose, sucrose andlactose: polysaccharides such as starch, cellulose powder and dextrin;organic substances such as urea, urea derivatives, benzoic acid andbenzoic acid salts; plants such as wood flour, powdered cork, corncob,walnut shell and tobacco stems, fly ash, white carbon (such as hydratedsynthetic silica, anhydrous synthetic silica and hydrous syntheticsilicate), fertilizers and the like may be mentioned.

As liquid carriers, aromatic hydrocarbons such as xylene, alkyl (C₉ orC₁₀ etc.) benzene, phenylxylylethane and alkyl (C₁ or C₃ etc.)naphthalene; aliphatic hydrocarbons such as machine oil, normalparaffin, isoparaffin and naphthene; mixtures of aromatic hydrocarbonsand aliphatic hydrocarbons such as kerosene; alcohols such as ethanol,isopropanol, cyclohexanol, phenoxyethanol and benzyl alcohol; polyhydricalcohols such as ethylene glycol, propylene glycol, diethylene glycol,hexylene glycol, polyethylene glycol and polypropylene glycol; etherssuch as propyl cellosolve, butyl cellosolve, phenyl cellosolve,propylene glycol monomethyl ether, propylene glycol monoethyl ether,propylene glycol monopropyl ether, propylene glycol monobutyl ether andpropylene glycol monophenyl ether; ketones such as acetophenone,cyclohexanone and γ-butyrolactone; esters such as fatty acid methylesters, dialkyl succinates, dialkyl glutamate, dialkyl adipates anddialkyl phthalates; acid amides such as N-alkyl (C₁, C₈ or C₁₂ etc.)pyrrolidone; fats and oils such as soybean oil, linseed oil, rapeseedoil, coconut oil, cottonseed oil and castor oil; dimethyl sulfoxide;water and the like may be mentioned.

These solid and liquid carriers may be used alone or in combinations oftwo or more.

As surfactants, nonionic surfactants such as polyoxyethylene alkylether, polyoxyethylene alkyl (mono or di) phenyl ether,polyoxyethylene(mono, di or tri)styrylphenyl ether,polyoxyethylenepolyoxypropylene block copolymers, polyoxyethylene fattyacid (mono or di) ester, sorbitan fatty acid ester, polyoxyethylenesorbitan fatty acid ester, ethylene oxide adducts of castor oil,acetylene glycol, acetylene alcohol, ethylene oxide adducts of acetyleneglycol, ethylene oxide adducts of acetylene alcohol and alkylglycosides; anionic surfactants such as alkyl sulfate salts,alkylbenzenesulfonic acid salts, lignin sulfonate, alkylsulfosuccinicacid salts, naphthalenesulfonic acid salts, alkylnaphthalenesulfonicacid salts, salts of naphthalenesulfonic acid-formalin condensates,salts of alkylnaphthalenesulfonic acid-formalin condensates,polyoxyethylene alkyl ether sulfate or phosphate salts, polyoxyethylene(mono or di) alkylphenyl ether sulfate or phosphate salts,polyoxyethylene (mono, di or tri) styrylphenyl ether sulfate orphosphate salts, polycarboxylic acid salts (such as polyacrylates,polymaleates and copolymers of maleic acid and an olefin) andpolystyrenesulfonic acid salts; cationic surfactants such as alkylaminesalts and alkyl quaternary ammonium salts; amphoteric surfactants suchas amino acid types and betaine types, silicone surfactants; andfluorine surfactants may be mentioned.

The amount of these surfactants is usually preferably from 0.05 to 20parts by weight per 100 parts by weight of the agent of the presentinvention, though there is no particular restrictions. These surfactantsmay be used alone or in combination of two or more.

The suitable application dose of the compounds of the present inventionis generally about from 0.005 to 50 kg per hectare (ha) in terms of theactive ingredient, though it varies depending on the applicationsituation, the application season, the application method and thecultivated crop.

When the compounds of the present invention are used to control externalor internal parasites in or on mammals and birds as farm animals/poultryand pet animals, the compounds of the present invention may beadministered in an effective amount together with pharmaceuticallyacceptable additives orally, parenterally by injection (intramuscular,subcutaneously, intravenously or intraperitoneally); percutaneously bydipping, spraying, bathing, washing, pouring-on and spotting-on anddusting, or intranasally. The compounds of the present invention may beadministered through molded articles such as chips, plates, bands,collars, ear marks, limb bands and ID tags.

The compounds of the present invention are administered in an arbitrarydosage form suitable for the administration route.

In a case where the compounds of the present invention are used tocontrol external or internal parasites, the suitable application dose ofthe compound (1) of the present invention as an active ingredient isgenerally from 0.01 to 100 mg/kg body weight, preferably from 0.01 to 50mg/kg body weight of a target animal, though it varies depending on e.g.the type of pests to be controlled, the type of the target animal, orthe application method. Particularly with respect to application to adog, the suitable application dose is generally from 1 to 5,000 mg/kgbody weight, preferably from 1 to 100 mg/g body weight of a target dog,though it varies depending on the type or the age of the target dog, orthe external parasites to be controlled.

In a case where the compounds of the present invention are used tocontrol external or internal parasites, the application interval may beoptionally set usually within a range of from daily to annually, thoughit varies depending on e.g. the type of pests to be controlled, the typeof the target animal, or the application method. The applicationinterval is preferably from once a week to every six months, morepreferably daily (every 24 hours), monthly, once a month, every twomonths, every three months, or every six months.

In a case where the compounds of the present invention are used tocontrol external parasites on a dog, with respect to the timing ofapplication of the compound of the present invention to the dog, thecompound of the present invention may be orally administered to the dog30 minutes before start of feeding or 120 minutes after completion offeeding. “30 minutes before start of feeding or 120 minutes aftercompletion of feeding” here is based on an action of the dog to takenutritious food. For example, in a case where the dog feeding time is 20minutes, the time specified is 30 minutes before start of feeding to 120minutes after completion of feeding, that is, 170 minutes in total. Acase where feeding is suspended, the compound of the present inventionis orally administered and feeding is restarted, is included. In thisspecification, feeding means an action of an animal to take food.

The number of feeding of a dug is usually three to four times a day inthe case of a dog of less than six months old, twice to three times aday in the case of a dog of six months to less than one year old, twicea day in the case of an adult dog of about one to five years old, andtwice to three times a day in the case of an old dog of 6 years old orolder, though it varies depending on the type or the age of the dog orthe habit. In the present invention, feeding means an action of ananimal to take nutritious food, and does not include an action to givefood and the like to a dog for training or breeding.

The dosage form may be a solid preparation such as dusts, granules,wettable powders, pellets, tablets, boluses, capsules and a moldedarticle containing an active ingredient; a liquid preparation such as aninjection fluid, an oral liquid, a liquid preparation applied to theskin or coelom; a solution preparation such as a pour-on preparation, aspot-on preparation, flowables and emulsions; and a semisolidpreparation such as an ointment and gels.

In a case where the compounds of the present invention are orallyadministered, the dosage form may, for example, be a solid preparationsuch as tablets, chewables, capsules, pills, boluses, granules andpowders; a semisolid preparation such as pastes and gels; and a liquidpreparation such as drinks.

In the case of percutaneous administration, the dosage form may, forexample, be a solid preparation such as powders; a semisolid preparationsuch as a cream, a salve and ointment, pastes and gels; and a liquidpreparation such as a spray, aerosols, solutions and emulsions,suspensions, and lotions.

Further, in the case of administration by injection, the dosage formmay, for example, be a liquid preparation such as solutions andemulsions, and suspensions, and in the case of intranasaladministration, the dosage form may, for example, be a liquidpreparation such as aerosols. In the case of spraying over anenvironment where animals are bred, such as a stable, the dosage formmay, for example, be a solid preparation such as wettable powders, dustsor granules; and a liquid preparation such as emulsions and suspensionconcentrates.

The formulation to be used for parasiticides of the present invention isnot limited to such dosage forms.

The solid preparation may be orally administered as it is, or may bepercutaneously administered or sprayed over an environment where animalsare bred, such as a stable, after dilution with water.

The solid preparation to be orally administered, may be prepared bymixing the compound represented by the formula (1) or its salt and oneor more vehicles or binders suitable for oral administration, and as thecase requires, physiologically acceptable additives such as a lubricant,a disintegrant, a dye and a pigment, and forming the mixture into adesired shape.

The vehicle and the binder may, for example, be a saccharide orsaccharide derivative such as lactose, sucrose, mannitol or sorbitol; astarch such as corn starch, wheat starch, rice starch or potato starch;a cellulose or cellulose derivative such as methyl cellulose,carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl celluloseor hydroxypropylmethyl cellulose; a protein or protein derivative suchas zein or gelatin; honey, gum arabic glue, or a synthetic polymercompound such as polyvinyl alcohol or polyvinyl pyrrolidone.

The lubricant may, for example, be magnesium stearate, and thedisintegrant may, for example, be cellulose, agar, alginic acid,crosslinked polyvinyl pyrrolidone or a carbonate.

Among solid preparations to be orally administered, in the case of asolid formulation such as chewables, additives which impart a taste,texture or flavor desired by animals to which the preparation is to beadministered, may be used. The carriers and additives to be used for thesolid preparation of the parasiticidal composition of the presentinvention are not limited thereto.

The liquid preparation may be administered percutaneously or byinjection as it is, or may be administered orally by being mixed withfood, orally or percutaneously administered after being diluted withwater, or sprayed to an environment where animals are bred, such as astable.

An injection fluid may be administered intravenously, intramuscularly orsubcutaneously. An injection fluid can be prepared by dissolving anactive ingredient in an appropriate solvent and, if necessary, addingadditives such as a solubilizer, an acid, a base, a buffering salt, anantioxidant and a protectant.

As appropriate solvents, water, ethanol, butanol, benzyl alcohol,glycerin, propylene glycol, polyethylene glycol, N-methylpyrrolidone andmixtures thereof, physiologically acceptable vegetable oils, andsynthetic oils suitable for injection may be mentioned.

As solubilizers, polyvinylpyrrolidone, polyoxyethylated castor oil,polyoxyethylated sorbitan ester and the like may be mentioned.

As protectants, benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acidesters, n-butanol and the like may be mentioned.

An oral liquid may be administered directly or after dilution and can beprepared in the same manner as an injection fluid.

A flowable, an emulsion or the like may be administered directly orafter dilution percutaneously or by environmental application.

A liquid preparation applied to the skin is administered by dripping,spreading, rubbing, spraying, sprinkling or dipping (soaking, bathing orwashing) and can be prepared in the same manner as an injection fluid.

A pour-on preparation and a spot-on preparation are dripped or sprayedto a limited area of the skin so that they permeate through the skin andact systemically. A pour-on preparation and a spot-on preparation can beprepared by dissolving, suspending or emulsifying an active ingredientin an appropriate skin-friendly solvent or solvent mixture. Ifnecessary, additives such as a surfactant, a colorant, anabsorbefacient, an antioxidant, a light stabilizer and an adhesive maybe added.

As appropriate solvents, water, alkanol, glycol, polyethylene glycol,polypropylene glycol, glycerin, benzyl alcohol, phenylethanol,phenoxyethanol, ethyl acetate, butyl acetate, benzyl benzoate,dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether,acetone, methyl ethyl ketone, aromatic and/or aliphatic hydrocarbons,vegetable or synthetic oils, DMF (N,N-dimethylformamide), liquidparaffin, light liquid paraffin, silicone, dimethylacetamide,N-methylpyrrolidone or 2,2-dimethyl-4-oxy-methylene-1,3-dioxolane may bementioned.

As absorbefacients, DMSO (dimethyl sulfoxide), isopropyl myristate,pelargonic acid dipropylene glycol, silicone oil, fatty acid esters,triglycerides and aliphatic alcohols may be mentioned.

As antioxidants, sulfites, metabisulfites, ascorbic acid,butylhydroxytoluene, butylhydroxyanisole and tocopherol may bementioned.

An emulsion may be administered orally, percutaneously or by injection.An emulsion can be prepared by dissolving an active ingredient in ahydrophobic phase or a hydrophilic phase and homogenizing the resultingsolution with another liquid phase together with an appropriateemulsifier, and further if necessary with additives such as a colorant,an absorbefacient, a protectant, an antioxidant, a light screen and athickener.

As hydrophobic phases (oils), paraffin oil, silicone oil, sesame oil,almond oil, castor oil, synthetic triglycerides, ethyl stearate,di-n-butyryl adipate, hexyl laurate, pelargonic acid dipropylene glycol,esters of branched short-chain fatty acids with C₁₆-C₁₈ saturated fattyacids, isopropyl myristate, isopropyl palmitate, esters of C₁₂-C₁₈saturated alcohols with caprylic/capric acid, isopropyl stearate, oleyloleate, decyl oleate, ethyl oleate, ethyl lactate, fatty acid esterwaxes, dibutyl phthalate, diisopropyl adipate, isotridecyl alcohol,2-octyldodecanol, cetylstearyl alcohol and oleyl alcohol may bementioned.

As hydrophilic phases, water, propylene glycol, glycerin and sorbitolmay be mentioned.

As emulsifiers, nonionic surfactants such as polyoxyethylated castoroil, polyoxyethylated sorbitan monoolefinic acid, sorbitan monostearate,glycerin monostearate, polyoxyethyl stearate and alkyl phenol polyglycolether; amphoteric surfactants such as disodiumN-lauryl-β-iminodipropionate and lecithin; anionic surfactants such assodium lauryl sulfate, aliphatic alcohol sulfate ether andmono/dialkylpolyglycol orthophosphate monoethanolamine salt; andcationic surfactants such as cetyltrimethylammonium chloride may, forexample, be mentioned.

As other additives, carboxymethylcellulose, methylcellulose,polyacrylate, alginate, gelatin, gum arabic, polyvinylpyrrolidone,polyvinyl alcohol, methyl vinyl ether, maleic anhydride copolymers,polyethylene glycol, waxes and colloidal silica may be mentioned.

A semisolid preparation is administered by applying or spreading ontothe skin or introducing into the coelom. A gel can be prepared by addinga thickener to a solution prepared in the same manner as an injectionfluid sufficiently to give a transparent viscous substance like anointment.

Next, Formulation Examples of preparations using the compounds of thepresent invention are given below. However, formulations of the presentinvention are by no means restricted thereto. In the followingFormulation Examples, “parts” means parts by weight.

[Wettable Powder]

Compound of the present invention 0.1 to 80 parts Solid carrier 5 to98.9 parts Surfactant 1 to 10 parts Others 0 to 5 parts

As the others, an anti-caking agent, a stabilizer and the like may bementioned.

[Emulsifiable Concentrate]

Compound of the present invention 0.1 to 30 parts Liquid carrier 45 to95 parts Surfactant 4.9 to 15 parts Others 0 to 10 parts

As the others, a spreader, a stabilizer and the like may be mentioned.

[Suspension Concentrate]

Compound of the present invention 0.1 to 70 parts Liquid carrier 15 to98.89 parts Surfactant 1 to 12 parts Others 0.01 to 30 parts

As the others, an anti-freezing agent, a thickener and the like may bementioned.

[Water Dispersible Granule]

Compound of the present invention 0.1 to 90 parts Solid carrier 0 to98.9 parts Surfactant 1 to 20 parts Others 0 to 10 parts

As the others, a binder, a stabilizer and the like may be mentioned.

[Soluble Concentrate]

Compound of the present invention 0.01 to 70 parts Liquid carrier 20 to99.99 parts Others 0 to 10 parts

As the others, an anti-freezing agent, a spreader and the like may bementioned.

[Granule]

Compound of the present invention 0.01 to 80 parts Solid carrier 10 to99.99 parts Others 0 to 10 parts

As the others, a binder, a stabilizer and the like may be mentioned.

[Dustable Powder]

Compound of the present invention 0.01 to 30 parts Solid carrier 65 to99.99 parts Others 0 to 5 parts

As the others, an anti-drift agent, a stabilizer and the like may bementioned.

Next, more specific Formulation Examples of preparations containing thecompounds of the present invention as an active ingredient are givenbelow. However, the present invention is by no means restricted thereto.

[Formulation Example 1] Wettable Powder

Compound No. 1-1-001a of the present invention 20 parts Pyrophyllite 74parts Sorpol 5039  4 parts(tradename for a mixture of a nonionic surfactant and an anionicsurfactant: manufactured by TOHO Chemical Industry Co., Ltd.)

CARPLEX #80D 2 parts(tradename for hydrous synthetic silicic acid: manufactured by Shionogi& Co., Ltd.)

The above ingredients are mixed and pulverized homogenously to obtain awettable powder.

[Formulation Example 2] Emulsifiable Concentrate

Compound No. 1-1-001a of the present invention  5 parts Xylene 75 partsN-methylpyrrolidone 15 parts Sorpol 2680  5 parts(tradename for a mixture of a nonionic surfactant and an anionicsurfactant: manufactured by TOHO Chemical Industry Co., Ltd.)

The above ingredients are mixed homogenously to obtain an emulsifiableconcentrate.

[Formulation Example 3] Suspension Concentrate

Compound No. 1-1-001a 25 parts AGRISOL S-710 10 parts (tradename for anonionic surfactant: manufactured by Kao Corporation) Runox 1000C 0.5part (tradename for an anionic surfactant: manufactured by TOHO ChemicalIndustry Co., Ltd.) Xanthan gum 0.2 part Water 64.3 parts

The above ingredients are mixed homogenously and wet-pulverized toobtain a suspension concentration.

[Formulation Example 4] Water Dispersible Granule

Compound No. 1-1-001a of the present invention 75 parts HITENOL NE-15  5parts (tradename for an anionic surfactant: manufactured by DKS Co.,Ltd.) VANILLEX N 10 parts (tradename for an anionic surfactant:manufactured by Nippon Paper Industries Co., Ltd.) CARPLEX #80D 10 parts(tradename for hydrous synthetic silicic acid: manufactored by Shionogi& Co., Ltd.)

The above ingredients are mixed and pulverized homogenously, thenkneaded with a small amount of water, granulated through an extrusiongranulator and dried to obtain a water dispersible granule.

[Formulation Example 5] Granule

Compound No. 1-1-001a of the present invention  5 parts Bentonite 50parts Talc 45 parts

The above ingredients are mixed and pulverized homogenously, thenkneaded with a small amount of water, granulated through an extrusiongranulator and dried to obtain a granule.

[Formulation Example 6] Dustable Powder

Compound No. 1-1 -001a of the present invention 3 parts CARPLEX #80D 0.5part (tradename for a hydrous synthetic silidc acid: manufactured byShionogi & Co., Ltd.) Kaolinite 95 parts Diisopropyl phosphate 1.5 parts

The above ingredients are mixed and pulverized homogeneously to obtain adustable powder.

It is applied after diluted with water by a factor of from 1 to 10000 ordirectly without dilution.

[Formulation Example 7] Wettable Powder Preparation

Compound No. 1-1-001a of the present invention 25 parts Sodiumdiisobutylnaphthalenesulfonate 1 part Calcium n-dodecylbenzenesulfonate10 parts Alkyl aryl polyglycol ether 12 parts Naphthalenesulfonicacid-formalin condensate sodium salt 3 parts Silicone emulsion 1 partSilicon dioxide 3 parts Kaolin 45 parts

[Formulation Example 8] Water-Soluble Concentrate Preparation

Compound No. 1-1-001a of the present invention 20 partsPolyoxyethylenelauryl ether 3 parts Sodium dioctylsulfosuccinate 3.5parts Dimethyl sulfoxide 37 parts 2-Propanol 36.5 parts

[Formulation Example 9] Liquid Preparation for Spraying

Compound No. 1-1-001a of the present invention  2 parts Dimethylsulfoxide 10 parts 2-Propanol 35 parts Acetone 53 parts

[Formulation Example 10] Liquid Preparation for PercutaneousAdministration

Compound No. 1-1-001a of the present invention  5 parts Hexylene glycol50 parts Isopropanol 45 parts

[Formulation Example 11] Liquid Preparation for PercutaneousAdministration

Compound No, 1-1-001a of the present invention  5 parts Propylene glycolmonomethyl ether 50 parts Dipropylene glycol 45 parts

[Formulation Example 12] Liquid Preparation for PercutaneousAdministration (by Dripping)

Compound No. 1-1-001a of the present invention  2 parts Light liquidparaffin 98 parts

[Formulation Example 13] Liquid Preparation for PercutaneousAdministration (by Dripping)

Compound No. 1-1-001a of the present invention 2 parts Light liquidparaffin 58 parts Olive oil 30 parts ODO-H 9 parts Shin-etsu silicone 1part

For use as agricultural chemicals, the compounds of the presentinvention may be mixed with other herbicides, insecticides, acaricides,nematicides, fungicides, plant growth regulators, synergists,fertilizers, soil conditioners and the like at the time of formulationor application.

Particularly, the combined use with other agricultural chemicals orplant hormone is expected to reduce the cost by enabling control atlower doses, to broaden the insecticidal spectrum by the synergisticeffect of the other agrochemicals, and to achieve a higher pesticidaleffect. In such cases, they may be combined with a plurality of knownagricultural chemicals.

The agricultural chemicals to be used in combination with the compoundsof the present invention include, for example, the compounds disclosedin e.g. The Pesticide Manual, 15th edition, 2009, having the genericnames listed below, but are not necessarily restricted thereto.

Fungicides: acibenzolar-S-methyl, acylaminobenzamide, acypetacs,aldimorph, ametoctradin, amisulbrom, amobam, ampropyfos, anilazine,azaconazole, azithiram, azoxystrobin, barium polysulfide, benalaxyl,benalaxyl-M, benodanil, benomyl, benquinox, bentaluron,benthiavalicarb-isopropyl, benthiazole, benzamacril, benzamorf,benzovindiflupyr, bethoxazine, binapacryl, biphenyl, bitertanol,blasticidin-S, bixafen, bordeaux mixture, boscalid, bromuconazole,bupirimate, buthiobate, calcium polysulfide, calcium polysulfide,captafol, captan, carpropamid, carbamorph, carbendazim, carboxin,carvone, cheshunt mixture, chinomethionat, chlobenthiazone,chloraniformethane, chloranil, chlorfenazol, chloroneb, chloropicrin,chlorothalonil, chlorquinox, chlozolinate, climbazole, dotrimazole,copper acetate, copper carbonate, basic, copper hydroxide, coppernaphthenate, copper oleate, copper oxychloride, copper sulfate, coppersulfate, basic, copper zinc chromate, cufraneb, coumoxystrobin,cuprobam, cyazofamid, cyclafuramid, cycloheximide, cyflufenamid,cymoxanil, cypendazole, cyproconazol, cyprodinil, cyprofuram, dazomet,debacarb, decafentin, dehydroacetic acid, dichlofluanid, dichlone,dichlorophen, dichlozoline, diclobutrazol, diclocymet, diclomedine,dicloran, etc.

Fungicides (continued): diethofencarb, difenoconazole, diflumetorim,dimethirimol, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M,dinobuton, dinocap, dinocap-4, dinocap-6, dinocton, dinosulfon,dinoterbon, diphenylamine, dipymetitrone, dipyrithione, ditalimfos,dithianon, dodemorph-acetate, dodine, drazoxolon, edifenphos,enestrobin, enoxastrobin, epoxiconazole, etaconazole, ethaboxam, etem,ethirimol, ethoxyquin, etridiazole, famoxadone, fenarimol,fenbuconazole, fenamidone, fenaminosulf, fenaminstrobin, fenapanil,fendazosulam, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil,fenpropidin, fenpyrazamine, fenpropimorph, fentin, ferbam, ferimzone,fluazinam, fludioxonil, flufenoxystrobin, flumetover, flumorph,fluopicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin,fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil,flutriafol, fluxapyroxad, folpet, fosetyl-aluminium, fthalide,fuberidazole, furalaxyl, furametpyr, furcarbanil, furconazole,furconazole-cis, furmecyclox, furphanate, glyodin, griseofulvin,guazatine, halacrinate, hexachlorobenzene, hexaconazole, hexylthiofos,8-hydroxyquinoline sulfate, hymexazol, imazalil, imibenconazole,iminoctadine-albesilate, iminoctadine-triacetate, ipconazole,iprobenfos, iprodione, iprovalicarb, isofetamid, isoprothiolane,isopyrazam, isotianil, isovaledione, etc.

Fungicides (continued): kasugamycin, kresoxim-methyl, laminadin,mancopper, mancozeb, mandestrobin, mandipropamid, maneb, mebenil,mecarbinzid, mepanipyrim, meptyldinocap, mepronil, metalaxyl,metalaxyl-M, metam, metazoxolon, metconazole, methasulfocarb,methfuroxam, methyl isothiocyanate, metiram, metominostrobin,metrafenone, metsulfovax, milneb, mydobutanil, myclozolin, nabam,natamycin, nickel bis(dimethyldithiocarbamate), nitrostyrene,nitrothal-isopropyl, nuarimol, OCH, octhilinone, ofurace, orysastrobin,oxathiapiprolin, oxadixyl, oxine copper, oxycarboxin, oxpoconazolefumarate, pefurzoate, penconazole, penflufen, pencycuron, penthiopyrad,o-phenylphenol, phosdiphen, picarbutrazox, picoxystrobin, piperalin,polycarbamate, polyoxins, polyoxorim, potassium azide, potassiumhydrogen carbonate, proquinazid, probenazole, prochloraz, procymidone,propamocarb hydrochloride, propiconazole, propineb, prothiocarb,prothioconazole, pydiflumetofen, pyracarbolid, pyraclostrobin,pyrametostrobin, pyraoxystrobin, pyraziflumid, pyrazophos,pyribencarb-methyl, pyridinitril, pyrifenox, pyrimethanil,pyriminostrobin, pyrimorph, pyriofenone, pyrisoxazole, pyroquilon,pyroxychlor, pyroxyfur, quinomethionate, quinoxyfen, quintozene,quinacetol-sulfate, quinazamid, quinconazole, rabenzazole, Bacillussubtilis (Strain:D747, FZB24, GBO3, HA10404, MB1600, QST713, Y1336,etc.), etc.

Fungicides (continued): sedaxane, sodium azide, sodium hydrogencarbonate, sodium hypochlorite, sulfur, spiroxamine, salycylanilide,silthiofam, simeconazole, tebuconazole, tebufloquin, tecnazene, tecoram,tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide,thiochlorfenphim, thiophanate, thiophanate-methyl, thioquinox, thiram,tiadinil, tioxymid, tolciofos-methyl, tolprocarb, tolylfluanid,triadimefon, toriadimenol, triamiphos, triarimol, triazoxide,triazbutil, tributyltin oxide, trichlamide, tricyclazole, tridemorph,trifloxystrobin, triflumizole, triforine, triclopyricarb, triticonazole,validamycin, valifenalate, vinclozolin, zarilamide, zinc sulfate, zineb,ziram, zoxamide, shiitake mushroom mycelium extracts, shiitake mushroomfruiting body extracts, NF-180 (test name), MIF-1002 (test name), S-2399(test name), AKD-5195 (test name), etc.

Bactericides: benzalkonium chloride, bithionol, bronopol, cresol,formaldehyde, nitrapyrin, oxolinic acid, oxyterracycline, streptomycin,tecloftalam, etc.

Nematicides: aldoxycarb, bendothiaz, cadusafos, DBCP, dichlofenthion,DSP, ethoprophos, fenamiphos, fensulfothion, fluazaindolizine,fluensulfone, fosthiazate, fosthietan, imicyafos, isamidofos, isazofos,oxamyl, thiaxazafen, thionazin, tioxazafen, BYI-1921 (test name),MAI-08015 (test name), etc.

Acaricides: acequinocyl, acrinathrin, amidoflumet, amitraz, azocyclotin,BCI-033 (test name), benzoximate, bifenazate, bromopropylate,chinomethionat, chlorobezilate, clofentezine, cyenopyrafen,cyflumetofen, cyhexatine, dicofol, dienochlor, diflovidazin, DNOC,etoxazole, fenazaquin, fenbutatin oxide, fenothiocarb, fenpropathrin,fenpyroximate, fluacrypyrim, halfenprox, hexythiazox, milbemectin,propargite, pyflubumide, pyridaben, pyrimidifen, S-1870 (test name),spirodiclofen, spyromesifen, CL900167 (test name), tebufenpyrad, NA-89(test name), etc.

Insecticides: abamectin, acephate, acetamipirid, afidopyropen,afoxolaner, alanycarb, aldicarb, allethrin, azamethiphos,azinphos-ethyl, azinphos-methyl, Bacillus thuringiensis, bendiocarb,benfluthrin, benfuracarb, bensultap, bifenthrin, bioallethrin,bioresmethrin, bistrifluron, broflanilide, buprofezin, butocarboxim,carbaryl, carbofuran, carbosulfan, cartap, chlorantraniliprole,chlorethxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron,chlormephos, chloroprallethrin, chlorpyrifos, chlorpyrifos-methyl,chromafenozide, clothianidin, cyanophos, cyantranifiprole,cyclaniliprole, cycloprothrin, cyflumetofen, cyfluthrin,beta-cyfluthrin, cyhalodiamide, cyhalothrin, gamma-cyhalothrin,lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin,zeta-cypermethrin, cyphenothrin, cyromazine, deltamethrin, diacloden,diafenthiuron, diazinon, dicloromezotiaz, dichlorvos, diflubenzuron,dimefluthrin, dimethylvinphos, dinotefuran, diofenolan, disulfoton,dimethoate, emamectin-benzoate, empenthrin, endosulfan,alpha-endosulfan, EPN, esfenvalerate, ethiofencarb, ethiprole,etofenprox, etrimfos, fenitrothion, fenobucarb, fenoxycarb,fenpropathrin, fenthion, fenvalerate, fipronil, flonicamid, fluazuron,flubendiamide, flucycloxuron, flucythrinate, flufenerim, flufenoxuron,flufenprox, flumethrin, fluralaner, fluvalinate, tau-fluvalinate,fonophos, formetanate, formothion, furathiocarb, flufiprole, fluhexafon,flupyradifurone, flometoquin, etc.

Insecticides (continued): halofenozide, heptafluthrin, hexaflumuron,hydramethylnon, imidacloprid, imiprothrin, isofenphos, indoxacarb,indoxacarb-MP, isoprocarb, isoxathion, kappa-bifenthrin,kappa-tefluthrin, lepimectin, lufenuron, malathion, meperfluthrin,metaflumizone, metakldehyde, methamidophos, methidathion, methacrifos,metalcarb, methomyl, methoprene, methoxychlor, methoxyfenozide, methylbromide, metofluthrin, epsilon-metofluthrin, momfluorothrin,epsilon-momfluorothrin, monocrotophos, muscalure, nitenpyram, novaluron,noviflumuron, omethoate, oxydemeton-methyl, oxydeprofos, parathion,parathion-methyl, pentachlorophenol, permethrin, phenothrin, phenthoate,phoxim, phorate, phosalone, phosmet, phosphamidon, pirimicarb,pirimiphos-methyl, profenofos, profluthrin, prothiofos, propaphos,protrifenbute, pymetrozine, pyraclofos, pyrethrins, pyridalyl,pyrifluquinazon, pyriprole, pyrafluprole, pyriproxyfen, resmethrin,rotenone, SI-0405 (test name), sulprofos, silafluofen, spinetoram,spinosad, spiromesifen, spirotetramat, sulfoxaflor, sulfotep, SYJ-159(test name), tebfenozide, teflubenzuron, tefluthorin, terbufos,tetrachlorvinphos, tetramethrin, d-tetramethrin, tetramethylfluthrin,tetraniliprole, thiacloprid, thiocyclam, thiodicarb, thiamethoxam,thiofanox, thiometon, tolfenpyrad, tralomethrin, transfluthrin,triazamate, trichlorfon, triazuron, triflumezopyrim, triflumuron,vamidothion, fluxametamide, MIE-1209 (test name), ME5382 (test name),Praziquantel, Febantel, etc.

EXAMPLES

Now, the present invention will be described in further detail withreference to Synthetic Examples and Test Examples of the compounds ofthe present invention. However, the present invention is by no meansrestricted thereto.

The preparative medium pressure liquid chromatography used was apreparative medium pressure chromatograph (YFLC-Wprep manufactured byYamazen Science, Inc. flow rate: 18 ml/min, 40-μm silica gel column).

Chemical shift values of proton nuclear magnetic resonance (hereinafterreferred to as ¹H-NMR) in Synthetic Examples and Reference Examples weremeasured by using Me₄Si (tetramethylsilane) as a standard substance indeuterated chloroform solvent at 300 MHz (JNM-ECX300 or JNM-ECP300manufactured by JEOL Ltd.).

Reference symbols in ¹H-NMR chemical shift values have the followingmeanings. s: singlet, d: doublet, dd: double doublet, t: triplet, q:quartet, and m: multiplet.

Synthetic Example 1: Synthesis of2-[6-chloro-3-(ethylthio)pyrazolo[1,5-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine(Compound No. 1-1-001b of the Present Invention) Step 1: Synthesis of6-chloro-N-[2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl]pyrazolo[1,5-a]pyridine-2-carboxamide

To a mixed solution of 584 mg ofN²-methyl-5-(trifluoromethyl)pyridine-2,3-diamine and 5 ml of pyridine,at room temperature, 500 mg of6-chloropyrazolo[1,5-a]pyridine-2-carboxylic acid, 975 mg of1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and 31 mg of4-dimethylaminopyridine were successively added. After the addition, themixture was stirred at room temperature for 18 hours. After thecompletion of the reaction, 10 ml of water was added to the reactionmixture, and the precipitated solid was collected by filtration toobtain 500 mg of the desired product. The product was used in the nextstep 2 without further purification.

Step 2: Synthesis of2-(6-chloropyrazolo[1,5-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine

A mixed solution of 500 mg of the desired product obtained in step 1 and5 ml of acetic acid was stirred under reflux with heating for 3 hours.After the completion of the reaction. 10 ml of water was added to thereaction mixture at room temperature. The precipitated solid wascollected by filtration to obtain 306 mg of the desired product as abrown solid.

Melting point: 238 to 240° C.

¹H-NMR (CDCl₃): δ8.75-8.65 (m, 1H), 8.65-8.55 (m, 1H), 8.35-8.25 (m,1H), 7.65-7.55 (m, 1H), 7.40-7.35 (m, 1H), 7.20 (dd, J=9.6, 1.8 Hz, 1H),4.38 (s, 3H).

Step 3: Synthesis of2-[6-chloro-3-(ethylthio)pyrazolo[1,5-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine(Compound No. 1-1-001b of the Present Invention)

To a mixed solution of 929 mg of N-chlorosuccinimide and 6 ml of1,2-dichloroethane, at −30° C., 540 mg of ethanethiol was added. Afterthe addition, the mixture was stirred at room temperature for one hour.After the stirring, the reaction mixture was subjected to filtrationthrough Celite, and the Celite was washed with 2 ml of1,2-dichloroethane. To the resulting filtrate and washing liquid, 306 mgof the product obtained in Step 2 was added at room temperature. Afterthe addition, the mixture was stirred under reflux with heating for 6hours. After the completion of the reaction, the reaction mixture wasmixed with 10 ml of water and extracted with chloroform (10 ml×2). Theresulting organic layer was washed with 10 ml of a saturated sodiumhydrogen carbonate aqueous solution, dehydrated with saturated aqueoussodium chloride and dried over anhydrous sodium sulfate, and the solventwas evaporated under reduced pressure to obtain 200 mg of the desiredproduct as a brown solid.

Synthetic Example 2: Synthesis of2-[6-chloro-3-(ethylsulfonyl)pyrazolo[1,5-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine(Compound No. 1-1-001a of the Present Invention)

To a mixed solution of 200 mg of the compound No. 1-1-001b of thepresent invention obtained in Synthetic Example 1 and 5 ml ofchloroform, 184 mg of 65 mass % m-chloroperbenzoic acid (containingabout 30 mass % of water) was added under cooling with ice. After theaddition, the mixture was stirred at room temperature for 18 hours.After the completion of the reaction, the reaction mixture was mixedwith a saturated sodium thiosulfate aqueous solution and extracted with10 ml of chloroform. The resulting organic layer was washed with 10 mlof a 1 mol/L (liter) sodium hydroxide aqueous solution and dried overanhydrous sodium sulfate, and the solvent was evaporated under reducedpressure. The resulting residue was purified by preparative mediumpressure liquid chromatography [n-hexane:ethyl acetate with a gradientof from 100:0 to 0:100 (volume ratio, the same applies hereinafter)] toobtain 163 mg of the desired product as a white solid.

Melting point: 132 to 136° C.

¹H-NMR (CDCl₃): δ8.76 (d, J=1.8 Hz, 1H), 8.70-8.65 (m, 1H), 8.40-8.30(m, 2H), 7.60-7.50 (m, 1H), 4.12 (s, 3H), 3.93 (q, J=7.5 Hz, 2H), 1.39(t, J=7.5 Hz, 3H).

Synthetic Example 3: Synthesis of2-[3-(ethylsulfonyl)-6-(3-(trifluoromethyl)-1H-pyrazol-1yl)pyrazolo[1,5-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine(Compound No. 1-1-003a of the Present Invention)

To a mixed solution of 70 mg of2-[3-(ethylsulfonyl)-6-iodopyrazolo[1,5-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridineand 3 ml of N,N-dimethylformamide, at room temperature, 213 mg of cesiumcarbonate, 17 mg of N,N′-dimethylcyclohexane-1,2-diamine, 89 mg of3-(trifluoromethyl)-1H-pyrazole and 25 mg of copper(I) iodide weresuccessively added. After the addition, the atmosphere in the reactionvessel was replaced with nitrogen gas, and the mixture was stirred at90° C. for 4 hours.

After the completion of the reaction, the reaction mixture was mixedwith 10 ml of water and extracted with chloroform (10 ml×2). Theresulting organic layer was washed with 10 ml of a 1 mol/L sodiumhydroxide aqueous solution and dried over anhydrous sodium sulfate, andthe solvent was evaporated under reduced pressure. The resulting residuewas purified by preparative medium pressure liquid chromatography(n-hexane:ethyl acetate with a gradient of from 100:0 to 80:20) toobtain 32 mg of the desired product as a yellow solid.

Melting point: 226 to 229° C.

¹H-NMR (CDCl₃): δ9.17 (dd, J=2.0, 0.8 Hz, 1H), 8.80-8.76 (m, 1H), 8.52(dd, J=9.8, 0.8 Hz, 1H), 8.41-8.36 (m, 1H), 8.09-8.04 (m, 1H), 7.93 (dd,J=9.8, 2.0 Hz, 1H), 6.86 (d, J=2.7 Hz, 1H), 4.17 (s, 3H), 4.01 (q, J=7.5Hz, 2H), 1.42 (t, J=7.5 Hz, 3H).

Synthetic Example 4: Synthesis of2-[3-(ethylthio)-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine(Compound No. 1-1-004b of the Present Invention) Step 1: Synthesis of2-[3-iodo-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine

To a mixed solution of 210 mg of3-methyl-6-(trifluoromethyl)-2-[6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]-3H-imidazo[4,5-b]pyridineand 5 ml of N,N-dimethylformamide, at room temperature, 209 mg of1,3-diiodo-5,5-dimethylhydantoin was added. After the addition, themixture was stirred at 80° C. for 3 hours. After the completion of thereaction, 10 ml of a saturated sodium thiosulfate aqueous solution wasadded to the reaction mixture. The precipitated solid was collected byfiltration to obtain 205 mg of the desired product as a white solid.

¹H-NMR (CDCl₃): δ8.79-8.75 (m, 1H), 8.75-8.70 (m, 1H), 8.37-8.34 (m,1H), 7.90 (d, J=9.6 Hz, 1H), 7.53 (dd, J=9.6, 1.5 Hz, 1H), 4.43 (s, 3H).

Step 2: Synthesis of2-[3-(ethylthio)-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine(Compound No. 1-1-004b of the Present Invention)

To a mixed solution of 210 mg of the white solid obtained in Step 1 and5 ml of 1,4-dioxane, at room temperature, 158 mg ofdiisopropylethylamine, 14 mg of4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, 11 mg oftris(dibenzilideneacetone)dipalladium(0) and 30 mg of ethanethiol weresuccessively added. After the addition, the mixture was stirred underreflux with heating in a nitrogen atmosphere for 2 hours. After thecompletion of the reaction, the reaction mixture was mixed with 10 ml ofwater and extracted with chloroform (10 ml×2). The resulting organiclayer was dried over anhydrous sodium sulfate, and the solvent wasevaporated under reduced pressure. The resulting residue was purified bypreparative medium pressure liquid chromatography (n-hexane:ethylacetate with a gradient of from 100:0 to 50:50) to obtain 120 mg of thedesired product as a pale yellow solid.

¹H-NMR (CDCl₃) δ: 8.88 (d, J=1.5 Hz, 1H), 8.75 (d, J=1.2 Hz, 1H), 8.43(d, J=1.8 Hz, 1H), 7.99 (d, J=9.0 Hz, 1H), 7.46 (d, J=9.0 Hz, 1H), 4.22(s, 3H), 2.97 (q, J=7.5 Hz, 2H), 1.16 (t, J=7.5 Hz, 3H).

Synthetic Example 5: Synthesis of2-[3-(ethylthio)-6-(trifluoromethyl)-2H-indazol-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyrimidine(Compound No. 1-10-001b of the Present Invention) Step 1: Synthesis of3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-amine

To a mixed solution of 8.31 g of cyanogen bromide, 174 ml of water and174 ml of methanol, at room temperature, 5.0 g ofN²-methyl-5-(trifluoromethyl)pyridine-2,3-diamine was added. After theaddition, the mixture was stirred at 50° C. for 1 hour. After thecompletion of the reaction, the reaction mixture was adjusted to have apH of 8 with a 1 mol/L sodium hydroxide aqueous solution at roomtemperature, and the solvent was evaporated under reduced pressure. Theresulting residue was mixed with 100 ml of water and extracted with 100ml of ethyl acetate. The resulting organic layer was dehydrated withsaturated aqueous sodium chloride and dried over anhydrous sodiumsulfate, and the solvent was evaporated under reduced pressure to obtain3.48 g of the desired product as a purple solid.

¹H-NMR (CDCl₃): δ8.40-8.30 (m, 1H), 7.85-7.75 (m, 1H), 5.20-4.90 (brs,2H), 3.69 (s, 3H).

Step 2: Synthesis of3-methyl-6-(trifluoromethyl)-2-[6-(trifluoromethyl)-2H-indazol-2-yl]-3H-imidazo[4,5-b]pyridine

A mixed solution of 900 mg of the purple solid obtained in step 1, 829mg of 2-nitro-4-(trifluoromethyl)benzaldehyde and 10 ml of 2-propanolwas stirred under reflux with heating for 4 hours. After the stirring,to the mixture, 2.30 g of tributylphosphine was added at roomtemperature. After the addition, the reaction mixture was stirred underreflux with heating for 18 hours. After the completion of the reaction,the solvent was evaporated under reduced pressure. The resulting residuewas mixed with 10 ml of water and extracted with 10 ml of chloroform.The resulting organic layer was dried over anhydrous sodium sulfate, andthe solvent was evaporated under reduced pressure. The resulting residuewas purified by preparative medium pressure liquid chromatography(chloroform:methanol with a gradient of from 100:0 to 85:15) to obtain447 mg of the desired product as a pale yellow solid.

Melting point: 168 to 175° C.

¹H-NMR (CDCl₃): δ9.10 (s, 1H), 8.74 (s, 1H), 8.29 (s, 1H), 8.15 (s, 1H),7.90 (d, J=9.0 Hz, 1H), 7.35 (d, J=9.0 Hz, 1H), 4.42 (s, 3H).

Step 3: Synthesis of2-[3-chloro-6-(trifluoromethyl)-2H-indazol-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine

To a mixed solution of 397 mg of the pale yellow solid obtained in step2 and 10 mil of 1,2-dichloroethane, at room temperature, 274 mg ofN-chlorosuccinimide was added. After the addition, the mixture wasstirred under reflux with heating for 1.5 hours. After the stirring, tothe reaction mixture, 1,096 mg of N-chlorosuccinimide was added at roomtemperature. After the addition, the reaction mixture was stirred underreflux with heating for 1.5 hours. After the completion of the reaction,the solvent was evaporated under reduced pressure. The resulting residuewas purified by preparative medium pressure liquid chromatography(chloroform:methanol with a gradient of from 100:0 to 85:15) to obtain284 mg of the desired product as a pale yellow solid.

¹H-NMR (CDCl₃): δ8.85-8.80 (m, 1H), 8.45-8.40 (m, 1H), 8.09 (s, 1H),7.82 (d, J=9.3 Hz, 1H), 7.39 (d, J=9.3 Hz, 1H), 4.04 (s, 3H),

Step 4: Synthesis of2-[3-(ethylthio)-6-(trifluoromethyl)-2H-indazol-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine(Compound No. 1-10-001b of the Present Invention)

To a mixed solution of 284 mg of the pale yellow solid obtained in step3 and 1.3 ml of N,N-dimethylformamide, at room temperature, 85 mg ofsodium ethanethiolate was added. After the addition, the mixture wasstirred at 70° C. for 4 hours. After the completion of the reaction, thereaction mixture was mixed with 5 ml of water and extracted withchloroform (5 ml×2). The resulting organic layer was dried overanhydrous sodium sulfate, and the solvent was evaporated under reducedpressure. The resulting residue was purified by preparative mediumpressure liquid chromatography (chloroform:methanol with a gradient offrom 95:5 to 90:10) to obtain 86 mg of the desired product as a paleyellow solid.

¹H-NMR (CDCl₃): δ8.84 (s, 1H), 8.39 (s, 1H), 8.31 (d, J=9.3 Hz, 1H),8.25 (s, 1H), 7.61 (d, J=9.3 Hz, 1H), 3.91 (s, 3H), 3.85 (q, J=7.5 Hz,2H), 1.46 (t, J=7.5 Hz, 3H).

Synthetic Example 6: Synthesis of2-[3-(ethylsulfonyl)-6-(trifluoromethyl)-2H-indazol-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine(Compound No. 1-10-001a of the Present Invention)

To a mixed solution of 86 mg of compound No. 1-10-001b of the presentinvention obtained in Synthetic Example 5 and 1.3 ml of chloroform, 76mg of 65 mass % m-chloroperbenzoic acid (containing about 30 mass % ofwater) was added at room temperature. After the addition, the mixturewas stirred at room temperature for 18 hours. After the completion ofthe reaction, the reaction mixture was mixed with 3 ml of a saturatedsodium thiosulfate aqueous solution and extracted with chloroform (5ml×2). The resulting organic layer was dried over anhydrous sodiumsulfate, and the solvent was evaporated under reduced pressure. Theresulting residue was purified by preparative medium pressure liquidchromatography (chloroform:methanol with a gradient of from 100:0 to90:10) to obtain 70 mg of the desired product as a pale yellow solid.

Melting point: 133 to 135° C.

¹H-NMR (CDCl₃): δ8.83 (d, J=1.8 Hz, 1H), 8.38 (d, J=1.5 Hz, 1H), 8.30(d, J=9.0 Hz, 1H), 8.25 (d, J=0.9 Hz, 1H), 7.60 (dd, J=9.0, 1.2 Hz, 1H),3.91 (s, 3H), 3.85 (q, J=7.2 Hz, 2H), 1.46 (t, J=7.2 Hz, 3H).

Synthetic Example 7: Synthesis of2-[3-(ethylthio)-6-nitro-2H-indazol-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine(Compound No. 1-10-002b of the Present Invention) Step 1: Synthesis of2-azido-N-[3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl]-4-nitrobenzamide

To a mixed solution of 248 mg of3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-amine, 159 mg of2-azide-4-nitrobenzoic acid, 445 mg of diisopropylethylamine and 5 ml ofN,N-dimethylformamide, 437 mg ofO-(7-azabenzotriazol-1-yl-)-N,N,N′,N′-tetramethyluroniumhexafluorophosphate (HATU) was added at room temperature. After theaddition, the mixture was stirred at room temperature for 48 hours.After the completion of the reaction, the reaction mixture was mixedwith 10 ml of water and extracted with ethyl acetate (10 ml×2). Theresulting organic layer was dehydrated with saturated aqueous sodiumchloride and dried over anhydrous sodium sulfate, and the solvent wasevaporated under reduced pressure. The resulting residue was purified bypreparative medium pressure liquid chromatography (n-hexane:ethylacetate with a gradient of from 100:0 to 0:100) to obtain 175 mg of thedesired product as an orange solid.

¹H-NMR (CDCl₃): δ8.65-8.55 (m, 1H), 8.22 (d, J=8.4 Hz, 1H), 8.08 (d,J=2.0 Hz, 1H), 8.03 (dd, J=8.4, 2.0 Hz, 1H), 7.85-7.75 (m, 1H), 3.83 (s,3H) (No signal assigned to proton of NH was observed).

Step 2: Synthesis of2-[3-chloro-6-nitro-2H-indazol-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine

To 175 mg of the orange solid obtained in step 1, at room temperature, 3g of phosphorus oxychloride was added. After the addition, the mixturewas stirred at 100° C. for 2 hours. After the completion of thereaction, the reaction mixture was cooled to room temperature. Thereaction mixture was added dropwise to ice water, and the mixture wasextracted with chloroform (20 ml×2). The resulting organic layer wasdried over anhydrous sodium sulfate, and the solvent was evaporatedunder reduced pressure. The resulting residue was purified bypreparative medium pressure liquid chromatography (n-hexane:ethylacetate with a gradient of from 100:0 to 0:100) to obtain 102 mg of thedesired product as a yellow solid.

¹H-NMR (CDCl₃): δ8.83 (d, J=1.5 Hz, 1H), 8.75 (d, J=1.8 Hz, 1H), 8.45(d, J=1.5 Hz, 1H), 8.03 (dd, J=9.6, 1.8 Hz, 1H), 7.86 (d, J=9.6 Hz, 1H),4.07 (s, 3H).

Step 3: Synthesis of2-[3-(ethylthio)-6-nitro-2H-indazol-2-yl]-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine(Compound No. 1-10-002b of the Present Invention)

To a mixed solution of 102 mg of the yellow solid obtained in step 2 and2 ml of 1,4-dioxane, 80 mg of diisopropylethylamine, 30 mg of4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, 24 mg oftris(dibenzilideneacetone)dipalladium(0) and 19 mg of ethanethiol weresuccessively added at room temperature. After the addition, the mixturewas stirred under reflux with heating in a nitrogen atmosphere for 2hours. After the completion of the reaction, the reaction mixture wasmixed with 10 ml of water and extracted with chloroform (10 ml×2). Theresulting organic layer was dried over anhydrous sodium sulfate, and thesolvent was evaporated under reduced pressure. The resulting residue waspurified by preparative medium pressure liquid chromatography(n-hexane:ethyl acetate with a gradient of from 100:0 to 70:30) toobtain 108 mg of the desired product as a yellow oil.

¹H-NMR (CDCl₃): δ8.85-8.75 (m, 2H), 8.44 (d, J=1.8 Hz, 1H), 8.06 (dd,J=9.2, 1.8 Hz, 1H), 7.98 (dd, J=9.2, 0.7 Hz, 1H), 3.91 (s, 3H), 3.10 (q,J=7.4 Hz, 2H), 1.24 (t, J=7.4 Hz, 3H).

Synthetic Example 8: Synthesis of2-[3-(ethylsulfonyl)-5-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]-7-(perfluoroethyl)imidazo[1,2-c]pyrimidine(Compound No. 1-3-001a of the Present Invention) Step 1: Synthesis ofethyl 3-iodo-5-(trifluoromethyl)pyrazolo[1,5-a]pyridine-2-carboxylate

To a mixed solution of 4.49 g of ethyl5-(trifluoromethyl)pyrazolo[1,5-a]pyridine-2-carboxylate and 60 ml ofN,N-dimethylformamide, 5.95 g of 1,3-diiodo-5,5-dimethylhydantoin wasadded at room temperature. After the addition, the mixture was stirredat 80° C. for 7 hours. After the completion of the reaction, thereaction mixture was mixed with water, and the precipitated solid wascollected by filtration. The obtained solid was dissolved in 40 ml ofchloroform, followed by washing with a saturated sodium thiosulfateaqueous solution and then with saturated sodium hydrogen carbonate. Theresulting organic layer was dried over anhydrous sodium sulfate, and thesolvent was evaporated under reduced pressure to obtain 6.11 g of thedesired product as a pale brown solid.

Melting point: 147 to 150° C.

¹H-NMR (CDCl₃): δ8.62 (d, J=7.2 Hz, 1H), 7.93 (s, 1H), 7.11 (dd, J=7.2,2.0 Hz, 1H), 4.54 (q, J=7.2 Hz, 2H), 1.49 (t, J=7.2 Hz, 3H).

Step 2: Synthesis of3-(ethylthio)-5-(trifluoromethyl)pyrazolo[1,5-a]pyridine-2-carboxylicAcid

To a mixed solution of 6.11 g of the pale brown solid obtained in step 1and 50 ml of 1,4-dioxane, 6.17 g of diisopropylethylamine, 920 mg of4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, 728 mg oftris(dibenzilideneacetone)dipalladium(0) and 1.48 g of ethanethiol weresuccessively added. After the addition, the atmosphere in the reactionvessel was replaced with nitrogen gas, and the mixture was stirred underreflux with heating for 2 hours. After the completion of the reaction,the reaction mixture was subjected to filtration through Celite, and theCelite was washed with 50 ml of 1,4-dioxane. The resulting filtrate andwashing liquid were put together, and the solvent was evaporated underreduced pressure to obtain crude ethyl3-(ethylthio)-5-(trifluoromethyl)pyrazolo[1,5-a]pyridine-2-carboxylate.To a mixed solution of the obtained crude ethyl3-(ethylthio)-5-(trifluoromethyl)pyrazolo[1,5-a]pyridine-2-carboxylateand 50 ml of ethanol, 20 ml of a 1.5 mol/L sodium hydroxide aqueoussolution was added at room temperature. After the addition, the reactionmixture was stirred at room temperature for 3 hours. After thecompletion of the reaction, the solvent was evaporated under reducedpressure. The resulting residue was mixed with a 1 mol/L hydrochloricacid aqueous solution to adjust the aqueous layer to have a pH of 2, andextracted with chloroform (20 ml×2). The resulting organic layer wasdried over anhydrous sodium sulfate, and the solvent was evaporatedunder reduced pressure to obtain 4.73 g of the desired product as abrown solid.

Melting point: 195 to 205° C.

¹H-NMR (DMSO-d6): δ9.02 (d, J=7.2 Hz, 1H), 8.11 (s, 1H), 7.39 (d, J=7.2Hz, 1H), 2.85 (q, J=7.2 Hz, 2H), 1.06 (t, J=7.2 Hz, 3H) (No signalassigned to proton of CO₂H was observed).

Step 3: Synthesis of3-(ethylthio)-N-methoxy-N-methyl-5-(trifluoromethyl)pyrazolo[1,5-a]pyridine-2-carboxamide

To a mixed solution of 2.70 g of the brown solid obtained in step 2 and60 ml of dichloromethane, 2.95 g of oxalyl chloride and 30 mg ofN,N-dimethylformamide were successively added under cooling with ice.After the addition, the mixture was stirred at room temperature for 5hours. After the stirring, the solvent was evaporated from the reactionmixture under reduced pressure to obtain crude3-(ethylthio)-5-(trifluoromethyl)pyrazolo[1,5-a]pyridine-2-carboxylicacid chloride. A mixed solution of the obtained crude3-(ethylthio)-5-(trifluoromethyl)pyrazolo[1,5-a]pyridine-2-carboxylicacid chloride and 20 ml of dichloromethane was added under cooling withice to a mixed solution of 692 mg of N,O-dimethylhydroxylaminehydrochloride, 1.63 g of triethylamine and 20 ml of dichloromethaneprepared in a separate container. After the addition, the mixture wasstirred at room temperature for 16 hours. After the completion of thereaction, the reaction mixture was mixed with 10 ml of water andextracted with chloroform (10 ml×2). The resulting organic layer waswashed with a 1 mol/L hydrochloric acid aqueous solution and then with asaturated sodium hydrogen carbonate aqueous solution and dried overanhydrous sodium sulfate, and the solvent was evaporated under reducedpressure to obtain 1.98 g of the desired product as a brown oil.

¹H-NMR (CDCl₃): δ8.53 (d, J=7.2 Hz, 1H), 8.06 (s, 1H), 7.04 (dd, J=7.2,1.9 Hz, 1H), 3.71 (brs, 3H), 3.42 (s, 3H), 2.81 (q, J=7.2 Hz, 2H), 1.19(t, J=7.2 Hz, 3H).

Step 4: Synthesis of1-[3-(ethylthio)-5-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]ethan-1-one

In a nitrogen atmosphere, to a mixed solution of 1.98 g of the brown oilobtained in step 3 and 25 ml of tetrahydrofuran, 4.2 ml of a diethylether solution of about 3 mol/L methyl magnesium bromide (manufacturedby Tokyo Chemical Industry Co., Ltd.) was added under cooling with ice.After the addition, the mixture was stirred under cooling with ice for 1hour. After the completion of the reaction, the reaction mixture wasadded dropwise to 10 ml of a 4 mol/L hydrochloric acid aqueous solutionunder cooling with ice, and extracted with chloroform (20 ml×2). Theresulting organic layer was washed with a saturated sodium hydrogencarbonate aqueous solution, dehydrated with saturated aqueous sodiumchloride and dried over anhydrous sodium sulfate, and the solvent wasevaporated under reduced pressure to obtain 1.81 g of the desiredproduct as a brown solid.

Melting point 88 to 90° C.

-   -   ¹H-NMR (CDCl₃): δ8.53 (d, J=7.2 Hz, 1H), 8.12 (s, 1H), 7.09 (dd,        J=7.2, 2.0 Hz, 1H), 2.93 (q, J=7.5 Hz, 2H), 2.76 (s, 3H), 1.16        (t, J=7.5 Hz, 3H).

Step 5: Synthesis of1-[3-(ethylsulfonyl)-5-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]ethan-1-one

To a mixed solution of 1.75 g of the brown solid obtained in step 4 and20 ml of chloroform, 3.48 g of 65 mass % m-chloroperbenzoic acid(containing about 30 mass % of water) was added under cooling with ice.After the addition, the mixture was stirred at room temperature for 2hours. After the completion of the reaction, the reaction mixture wasmixed with 10 ml of a saturated sodium thiosulfate aqueous solution andextracted with chloroform (20 ml×2). The resulting organic layer waswashed with 20 ml of a 1 mol/L sodium hydroxide aqueous solution. Theorganic layer was dried over anhydrous sodium sulfate, and the solventwas evaporated under reduced pressure. The resulting residue waspurified by preparative medium pressure liquid chromatography(n-hexane:ethyl acetate with a gradient of from 100:0 to 50:50) toobtain 1.18 g of the desired product as a white solid.

Melting point: 123 to 125° C.

¹H-NMR (CDCl₃): δ8.72-8.68 (m, 1H), 8.64 (d, J=7.2 Hz, 1H), 7.28 (dd,J=7.2, 2.0 Hz, 1H), 3.71 (q, J=7.3 Hz, 2H), 2.77 (s, 3H), 1.33 (t, J=7.3Hz, 3H).

Step 6: Synthesis of2-bromo-1-[3-(ethylsulfonyl)-5-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]ethan-1-one

To a mixed solution of 1.15 g of the white solid obtained in step 5 and15 ml of toluene, 6.0 g of an acetic acid solution of about 5.1 mol/Lhydrogen bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) and631 mg of bromine were successively added at room temperature. After theaddition, the mixture was stirred at room temperature for 16 hours.After the completion of the reaction, the reaction mixture was mixedwith 10 ml of water and extracted with ethyl acetate (20 ml×2). Theresulting organic layer was washed with a 5 mass % sodium hydrogensulfite aqueous solution. The organic layer was dried over anhydroussodium sulfate, and the solvent was evaporated under reduced pressure toobtain 890 mg of the desired product as a white solid.

Melting point 204 to 206° C.

¹H-NMR (CDCl₃): δ8.72 (s, 1H), 8.65 (d, J=6.8 Hz, 1H), 7.33 (dd, J=6.8,2.0 Hz, 1H), 4.72 (s, 2H), 3.69 (q, J=7.3 Hz, 2H), 1.35 (t, J=7.3 Hz,3H).

Step 7: Synthesis of2-[3-(ethylsulfonyl)-5-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]-7-(perfluoroethyl)imidazo[1,2-c]pyrimidine(Compound No. 1-3-001a of the Present Invention)

To a mixed solution of 117 mg of 6-(perfluoroethyl)pyrimidin-4-amine and5 ml of chlorobenzene, 200 mg of the white solid obtained in step 6 wasadded at room temperature. After the addition, the mixture was stirredunder reflux with heating for 6 hours. After the completion of thereaction, the reaction mixture was mixed with 10 ml of a 1 mol/L sodiumhydroxide aqueous solution and extracted with ethyl acetate (10 ml×2).The resulting organic layer was dehydrated with saturated aqueous sodiumchloride and dried over anhydrous sodium sulfate, and the solvent wasevaporated under reduced pressure. The resulting residue was purified bypreparative medium pressure liquid chromatography (n-hexane:ethylacetate with a gradient of from 100:0 to 50:50) to obtain 44 mg of thedesired product as a white solid.

Melting point: 290 to 296° C.

¹H-NMR (CDCl₁): δ9.21 (s, 1H), 8.81 (s, 1H), 8.76 (d, J=7.2 Hz, 1H),8.65 (s, 1H), 8.05 (s, 1H), 7.30-7.28 (m, 1H), 3.48 (q, J=7.5 Hz, 2H),1.31 (t, J=7.5 Hz, 3H).

Synthetic Example 9: Synthesis of6-[3-(ethylsulfonyl)-5-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]-2-(perfluoroethyl)imidazo[2,1-b][1,3,4]thiadiazole(Compound No. 1-5-001a of the Present Invention)

To a mixed solution of 120 mg of5-(perfluoroethyl)-1,3,4-thiadiazol-2-amine and 5 ml of chlorobenzene,200 mg of the white solid obtained in step 6 in Synthetic Example 8 wasadded at room temperature. After the addition, the mixture was stirredunder reflux with heating for 6 hours. After the completion of thereaction, the reaction mixture was mixed with 10 ml of a 1 mol/L sodiumhydroxide aqueous solution and extracted with ethyl acetate (10 ml×2).The resulting organic layer was dehydrated with saturated aqueous sodiumchloride and dried over anhydrous sodium sulfate, and the solvent wasevaporated under reduced pressure. The resulting residue was purified bypreparative medium pressure liquid chromatography (n-hexane:ethylacetate with a gradient of from 100:0 to 50:50) to obtain 134 mg of thedesired product as a white solid.

Melting point 249 to 250° C.

¹H-NMR (CDCl₃): δ8.93 (s, 1H), 8.71 (d, J=7.2 Hz, 1H), 8.62 (s, 1H),7.24 (dd, J=7.2, 2.0 Hz, 1H), 3.46 (q, J=7.3 Hz, 2H), 1.31 (t, J=7.3 Hz,3H).

Synthetic Example 10: Synthesis of2-[3-(ethylthio)-5-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine(Compound No. 1-4-001b of the Present Invention) Step 1: Synthesis of1,2-diamino-4-(trifluoromethyl)pyridin-1-ium2,4,6-trimethylbenzenesulfonate

To 8.8 g of trifluoroacetic acid, 2.0 g of tert-butyl[(mesitylsulfonyl)oxy]carbamate was added under cooling with ice. Afterthe addition, the mixture was stirred under cooling with ice for 2hours. After the stirring, ice water was added to the reaction mixture.After the addition, the precipitated solid was collected by filtration.The obtained solid was dissolved in 20 ml of dichloromethane and driedover anhydrous sodium sulfate, and the anhydrous sodium sulfate wasremoved by filtration. To the obtained filtrate, 740 mg of4-(trifluoromethyl)pyridin-2-amine was added under cooling with ice.After the addition, the mixture was stirred at room temperature for 16hours. After the stirring, the solid precipitated in the reactionmixture was collected by filtration.

The obtained solid was washed with diethyl ether to obtain 1.1 g of thedesired product as a white solid.

Melting point: 202 to 205° C.

Step 2: Synthesis of2-[3-(ethylthio)-5-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine(Compound No. 1-4-001b of the Present Invention)

To a mixed solution of 90 mg of the white solid obtained in step 1 and 2ml of pyridine, 87 mg of3-(ethylthio)-5-(trifluoromethyl)pyrazolo[1,5-a]pyridine-2-carboxylicacid and 73 mg of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimidehydrochloride were successively added at room temperature. After theaddition, the mixture was stirred under reflux with heating for 5 hours.After the completion of the reaction, the solvent was evaporated underreduced pressure. The resulting residue was mixed with 20 ml of waterand extracted with ethyl acetate (20 ml×2). The resulting organic layerwas dehydrated with saturated aqueous sodium chloride and dried overanhydrous sodium sulfate, and the solvent was evaporated under reducedpressure. The resulting residue was purified by preparative mediumpressure liquid chromatography (n-hexane:ethyl acetate with a gradientof from 100:0 to 50:50) to obtain 40 mg of the desired product as a paleyellow solid.

¹H-NMR (CDCl₃): δ8.85 (d, J=7.2 Hz, 1H), 8.67 (d, J=7.2 Hz, 1H),8.21-8.13 (m, 2H), 7.29 (dd, J=7.2, 1.5 Hz, 1H), 7.08 (dd, J=7.2, 1.5Hz, 1H), 3.01 (q, J=7.5 Hz, 2H), 1.20 (t, J=7.5 Hz, 3H).

The compounds of the present invention may be synthesized in accordancewith the above Processes and Synthetic Examples. Examples of condensedheterocyclic compounds produced in the same manner as in SyntheticExamples 1 to 10 are shown in Tables 2 to 8, however, the condensedheterocyclic compounds of the present invention are not limited thereto.

In Tables, “Me” represents a methyl group, “Et” an ethyl group, and “Ph”a phenyl group. Further, in Tables, “*1” represents that the compound isa solid, “*2” represents that the compound is an oil or in a resinstate, and “m.p.” represents the melting point (unit: ° C.).

In Table, G2-2 represents the following cyclic structure, and the symbolin the bracket represents the number, the type and the substitutionposition of the substituent (Z²).

TABLE 2

No. R³ A^(1a) Y1 Y2 Y3 n m.p. 1-1-001a CF₃ Me H H Cl 2 132-136 1-1-001bCF₃ Me H H Cl 0 *1 1-1-002a CF₃ Me H H I 2 203-205 1-1-002b CF₃ Me H H I0 144-146 1-1-003a CF₃ Me H H G2-2[3-CF₃] 2 226-229 1-1-004a CF₃ Me H HCF₃ 2 *2 1-1-004b CF₃ Me H H CF₃ 0 *1 1-1-005a CF₃ Me H H Br 2 190-1921-1-005b CF₃ Me H H Br 0 *1 1-1-006a CF₃ Me H Cl H 2 216-217 1-1-006bCF₃ Me H Cl H 0 *1 1-1-007a CF₃ Me H Br H 2 226-229 1-1-007b CF₃ Me H BrH 2 *1 1-1-008a CF₃ Me H I H 2 236-238 1-1-009a CF₃ Me H Ph H 2 235-2371-1-010a CF₃ Me H H H 2 *2 1-1-011a CF₃ Me I H H 2 240-249 1-1-011b CF₃Me I H H 0 *1 1-1-012a CF₃ Me H CF₃ H 2 227-229 1-1-012b CF₃ Me H CF₃ H0 131-132 1-1-013a CF₃ Me H SMe H 2 164-166 1-1-014a CF₃ Me H SOMe H 2206-208 1-1-015a CF₃ Me H SO₂Me H 2 231-233 1-1-016a SCF₃ Me H CF₃ H 2210-212 1-1-016b SCF₃ Me H CF₃ H 0 127-129 1-1-017a SOCF₃ Me H CF₃ H 2210-212

TABLE 3

No. R³ A^(1a) Y1 Y2 Y3 n m.p. 1-2-001a CF₃ Me H H I 2 *1 1-2-001b CF₃ MeH H I 0 *1 1-2-002a CF₃ Me I H H 2 *2 1-2-002b CF₃ Me I H H 0 *1

TABLE 4

No. R³ R⁶ Y2 Y3 n m.p. 1-3-001a CF₂CF₃ H CF₃ H 2 290-296

TABLE 5

No. R³ Y2 Y3 n m.p. 1-4-001a CF₃ CF₃ H 2 *1 1-4-001b CF₃ CF₃ H 0 *1

TABLE 6

No. R³ R⁶ Y2 Y3 n m.p. 1-5-001a CF₂CF₃ H CF₃ H 2 249-250

TABLE 7

No. R³ A^(1a) Y2 Y3 n m.p. 1-10-001a CF₃ Me H CF₃ 2 133-135 1-10-001bCF₃ Me H CF₃ 0 *1 1-10-002a CF₃ Me H NO₂ 2 *2 1-10-002b CF₃ Me H NO₂ 0*2 1-10-003a CF₃ Me H I 2 *1 1-10-004a CF₃ Me H NH₂ 2 *2

TABLE 8

No. R³ A^(1a) Y2 Y3 n m.p. 1-11-001a CF₃ Me H CF₃ 2 238-240 1-11-001bCF₃ Me H CF₃ 0 144-146

Examples of production intermediates for production of the compounds ofthe present invention shown in Tables 1 to 8 are shown in Tables 9 to11, however, the production intermediates are not limited thereto.

In Tables, “Me” represents a methyl group.

TABLE 9

No. R³ A^(1a) Y1 Y2 Y3 J₁ m.p. i-1-001 CF₃ Me H H Cl H 238-240 i-1-002CF₃ Me H H I H *1 i-1-003 CF₃ Me H H Br H *1 i-1-004 CF₃ Me H H CF₃ H *1i-1-005 CF₃ Me H H CF₃ I *1 i-1-006 CF₃ Me H Cl H H 207-210 i-1-007 CF₃Me H Br H H 221-223 i-1-008 CF₃ Me H Cl H Cl 252-253

TABLE 10

No. R³ A^(1a) A⁴ A⁵ Y2 Y3 J₁ m.p. i-10-001 CF₃ Me CH N H CF₃ H 168-175i-10-002 CF₃ Me CH N H CF₃ Cl *1 i-10-003 CF₃ Me CH N H NO₂ Cl *1i-10-004 CF₃ Me N CH H CF₃ H *1 i-10-005 CF₃ Me N CH H CF₃ Cl 131-134

TABLE 11

No. R³ A^(1a) A⁴ A⁵ m.p. i-11-001 CF₃ Me CH N *1 i-11-002 CF₃ Me N CH152-154

¹H-NMR data of the compounds of the present invention and productionintermediates of which the melting point is not described, are shown inTable 12. The proton nuclear magnetic resonance chemical shift valueswere measured by using Me₄ Si (tetramethylsilane) as a standardsubstance in deuterated chloroform solvent at 300 MHz (ECX300 or ECP300,manufactured by JEOL Ltd.).

Reference symbols in the proton nuclear magnetic resonance chemicalshift values have the following meanings.

s: singlet, brs: broad singlet, d: doublet, dd: double doublet, t:triplet, q: quartet, m: multiplet

TABLE 12 No. ¹H NMR (CDCl₃, Mo₄Si, 300 MHz). 1-1-002a δ 8.92-8.88(m,1H), 8.77-8.73(m, 1H), 8.36(d, J = 1.8 Hz, 1H), 8.15(dd, J = 9.6, 0.6Hz, 1H), 7.71(dd, J = 9.6, 1.5 Hz, 1H), 4.11(s, 3H), 3.93(q, J = 7.5 Hz,2.H), 1.39(t, J = 7.5 HZ, 3H). 1-1-002b δ 8.83-8.80(m, 1H), 8.75-8.71(m,1H), 8.42-8.39(m, 1H), 7.66(dd, J = 9.3, 1.2 Hz, 1H), 7.80(dd, J = 9.3,1.2 Hz, 1H), 4.18(s, 3H), 2.92(q, J = 7.2 Hz, 2H), 1.13(t, J = 7.2 Hx, 3H). 1-1-004a δ 8.9(s, 1H), 8.80-8.76(m, 1H), 8.52(d, J = 9.6, 1H),8.39(d, J = 1.8 Hz, 1H), 7.70(d, J = 9.6 Hz, 1H), 4.16(s, 3H), 3.99(q, J= 7.5 Hz, 2H), 1.42(t, J = 7.5 Hz, 3H). 1-1-005a δ 8.79-8.73 (m, 2H),8.38-8.34(m, 1H), 8.28(dd, J = 10.5, 0.9 Hz, 1H), 7.62(dd, J = 9.3, 1.5Hz, 1H), 4.12(s, 3H), 3.94(q, J = 7.5 Hz, 2H), 1.39(t, J = 7.5 Hz, 3H).1-1-005b δ 8.74-8.71(m, 1H), 8.69-8.67(m, 1H). 8.40(d, J = 2.1 Hz, 1H),7.76(dd, J = 9.0, 0.6Hz, 1H), 7.39(dd, J = 9.6, 1.8 Hz, 1H), 4.18(s,3H), 2.92(q, J = 7.5 Hz, 2H), 1.13(t, J = 7.5 Hz, 3H). 1-1-006a δ8.79-8.70 (m, 1H), 8.53 (dd, J = 7.4, 0.6 Hz, 1H), 8.40-8.27 (m, 2H),7.13 (dd, J = 7.4, 2.1 Hz, 1H), 4.12 (s, 3H), 3.93 (q, J.= 7.5 Hz, 2H)1.41 (t, J = 7.5 Hz, 3H). 1-1-006b δ 8.74 (s, 1H), 8.49-8.36 (m, 2H),7.85 (d, J = 2.0 Hz, 1H), 6.94 (dd, J = 7.5, 2.0 Hz, 1H), 4.18 (s, 3H),2.91 (q, J = 7.5 Hz, 2H), 1.15 (t, J = 7.5 Hz, 3H). 1-1-007a δ 8.79-8.74(m, 1H), 8.57 (dd, J = 2.2, 0.9 Hz, 1H), 8.48-8.43 (m, 1H), 8.40-8.34(m, 1H), 7.27-7.24 (m, 1H), 4.12 (s, 3H), 3.92 (q, J = 7.2 Hz, 2H), 1.41(t, J = 7.2 Hz, 3H). 1-1-007b δ 8.74 (s, 1H), 8.50-8.35 (m, 2H),8.10-8.00 (m, 1H), 7.13-7.00 (m, 1H), 4.18 (s, 3H), 2.92 (q, J = 7.5 Hz,2H), 1.14 (t, J = 7.5 HZ, 3H). 1-1-008a δ 8.81-8.73 (m, 2H), 8.40-8.27(m, 2H), 7.44-7.37 (m, 1H), 4.11 (s, 3H), 3.91 (q, J = 7.5 Hz, 2H), 1.41(t, J = 7.5 Hz, 3H). 1-1-009a δ 8.76 (d, J = 1.7 Hz, 1H), 8.65 (d, J =7.2 Hz, 1H), 8.54-8.48 (m, 1H), 8.37 (d, .J = 1.7 Hz, 1H). 8.28-8.23 (m,1H), 7.77-7.73 (m, 1H), 7.63-7.40 (m, 4H), 4.13 (s, 3H), 3.89 (q, J =7.5 Hz, 2H), 1.42 (t, J = 7.5 Hz, 3H). 1-1-010a δ 8.80-8.75 (m, 1H),8.67-8.59 (m, 1H), 8.42-8.33 (m, 2H), 7.62-7.53 (_(m), 1H), 7.22-7.14(m, 1H), 4.12 (s, 3H), 3.88 (q, J = 7.5 Hz, 2H), 1.39 (t, J = 7.5 Hz,3H). 1-1-011a δ 8.77-8.73(m, 1H), 8.70(dd, J = 7.2, 1.2 Hz, 1H),8.35-8.32(m, 1H), 8.26(dd, J = 7.8, 1.5 Hz, 1H), 6.93 (dd, J = 6.9, 6.9Hz, 1H), 3.90(s, 3H), 3.72(q, J = 7.5 Hz, 2H), 1.44(t, J = 7.5 Hz, 3H).1-1-011b δ 8.76-8.72(m, 1H), 8.57(d, J = 6.2 Hz, 1H), 8.40(d, J = 2.1Hz, 1H), 7.91(d, J = 6.9 Hz, 1H), 6.71(dd, J = 7.2, 7.2 Hz, 1H), 4.05(s,3H). 2.84(q, J = 7.5.Hz, 2H), 1.13(t, J = 7.5 Hz, 3H). 1-2-001a δ(s,1H), 8.91(d, J = 0.9 Hz, 1H), 8.16(s, 1H), 8.14(d, J = 9.6 Hz, 1H), 7.75(dd, J = 9.6, 1.2 Hz, 1H), 4.13(s, 3H), 3.86(q, J = 7.5 Hz, 2H), 1.38(t,J = 7.5 Hz, 3H). 1-1-012a δ 8.81-8.67 (m, 3H), 8.39 (d, J = 2.0 Hz, 1H),7.33 (dd, J = 7.5, 2.0 Hz, 1H), 4.15 (s, 3H), 4.00 (q_(,) J = 7.2 Hz,2H), 1.43 (t, J = 7.2 Hz, 3H). 1-1-012b δ 8.77-8.73 (m, 1H), 8.63 (d, J= 7.2 Hz, 1H), 8.45-8.40 (m, 1H), 8.25-8.16 6 (m, 1H), 7.13 (dd, J =7.2, 2.0 Hz, 1H), 4.21 (s, 3H), 2.98 (q, J = 7.2 Hz, 2H), 1.16 (t, J =7.2 Hz, 3H). 1-1-013a δ 8.77-8.73 (m, 1H), 8.41-8.35 (m, 2H)_(,) 7.93(d, J = 2.0 Hz, 1H), 6.97 (dd, J = 7.2, 2.0 Hz, 1H), 4.10 (s, 3H), 3.87(q, J = 7.5 Hz, 2H) 2.63 (s, 3H), 1.4 (t, J = 7.5 Hz, 3H). 1-1-014a δ8.85-8.75 (m, 2H), 8.65-8.55 (m, 1H), 8.38 (d, J = 2.0 Hz, 1H), 7.54(dd, J = 7.2, 2.0 Hz, 1H), 4.16 (s, 3H), 4.09-3.86 (m, 2H), 2.88 (s_(,)3H), 1.42 (t, J = 7.5 Hz, 3H). 1-1-015a δ 9.08-8.95 (m, 1H), 8.84-8.73(m, 2H), 8.39 (d, J = 2.0 Hz, 1H), 7.62 (dd, J = 7.2, 2.0 Hz, 1H), 4.16(s, 3H), 4.02 (q, J = 7.5 Hz, 2H), 3.21 (s, 3H), 1.44 (t, J = 7.5 Hz,3H). 1-1-016a δ 8.80-8.67 (m, 3H), 8.45 (d, J = 2.0 Hz, 1H), 7.33 (dd, J= 7.2, .2.0 Hz, 1H), 4.14 (s, 3H), 4.01 (q, J = 7.2 Hz, 2H), 1.43 (t, J= 7.2 Hz, 3H). 1-1-016b δ 8.69 (d, J = 2.0 Hz, 1H), 8.62 (d, J = 7.2 Hz,1H), 8.49 (d, J = 2.0 Hz, 1H), 8.22-8.16 (m, 1H), 7.13 (dd, J = 7.2, 2.0Hz, 1H), 4.20 (s, 3H), 2.99, (q, J = 7.2 Hz, 2H), 1.17 (t, J = 7.2 Hz,3H). 1-1-017a δ 8.80 (d, J = 2.0 Hz, 1H) 8.77-8.66 (m, 2H), 8.62 (d, J =1.4 Hz, 1H), 7.35 (dd, J = 7.5, 2.0 Hz, 1H), 4.18 (s, 3H), 4.00 (q, J =7.2 Hz, 2H), 1.44 (t, J = 7.2 Hz, 3H). 1-2-001b δ 8.96(s, 1H),8.83-8.77(m, 1H), 8.24-8.19(m, 1H), 7.66(d, J = 9.3 Hz, 1H), 7.54-7.48(m, 1H), 4.20(s, 3H), 2.91(q, J = 7.5 Hz, 2H), 1.13(t, J = 7.5 Hz,3H). 1-2-002a δ 8.97(s, 1H), 8.70(dd, J = 6.9, 0.9 Hz, 1H), 8.27(dd, J =7.8, 1.2 Hz, 1H), 8.13(d, J = 0.9 Hz, 1H), 6.94 (dd, J = 6.9, 6.9 Hz,1H), 3.92(s, 3H), 3.70(q, J = 7.5 Hz, 2H), 1.42(t, J = 7.5 Hz, 3H).1-2-002b δ 8.97(s, 1H), 8.60-8.55(m, 1H), 8.20(s, 1H), 7.94-7.88(m, 1H),7.62(dd, J = 7.5, 7.5 Hz. 1H), 4.06(s, 3H), 2.81(q, J = 7.5 Hz, 2H),1.11(t, J = 7.5 Hz, 3H). 1-4-001a δ 8.88-8.72 (m, 3H), 8.20 (s, 1H),7.37-7.26 (m, 2H), 4.01 (q, J = 7,5 Hz, 2H), 1.43 (t, J=7.5 Hz, 3H).1-10-001b δ 8.84(s, 1H), 8.39(s, 1H), 8.31(d, J = 9.3 Hz, 1H), 8.25(s,1H), 7.61(d, J = 9.3 Hz, 1H), 3.91(s, 3H), 3.85(q, J = 7.5 Hz, 2H),1.46(t, J = 7.5 Hz, 3H). 1-10-002a δ 9.00-8.80(m, 2H), 8.40(d, J = 2.0Hz, 1H), 8.34(d, J = 9.6 Hz, 1H), 8.23(dd, J = 9.6, 1.8 Hz, 1H), 3.93(s,3H), 3.89(q, J = 7.5 Hz, 2H), 1.47(t, J = 7.5 Hz, 3H). 1-10-003a δ8.85-8.80(m, 1H), 8.40-8.30(m, 2H), 7.90(d, J = 9.0 Hz, 1H), 7.67(dd, J= 9.0, 1.2 Hz, 1H), 3.88(s, 3H), 3.82(q, J = 7.4 Hz, 2H), 1.43(t, J =7.4 Hz, 3H). 1-10-004a δ 8.80-8.75(m, 1H), 8.35-8.30(m, 1H), 7.94(d, J =9.6 Hz, 1H), 6.92(dd, J = 9.6, 1.8 Hz, 1H), 6.85-6.80(m, 1H),4.20-4.00(brs, 2H), 3.89(s, 3H), 3.80(q, J = 7.4 Hz, 2H), 1.43(t, J =7.4 Hz, 3H). 1-11-001a δ 9.06 (s, 1H), 8.34-8.28 (m, 1H), 8.25 (s, 1H),8.18 (s, 1H), 7.62 (dd, J = 9.0, 1.5 Hz, 1H), 3.93 (s, 3H), 3.83 (q, J =7.2 Hz, 2H), 1.46 (t, J = 7.2 Hz, 3H). 1-11-001b δ 9.03 (s, 1H), 8.22(s, 1H), 8.15 (s, 1H), 7.97 (d, J = 9.0 Hz, 1H), 7.43 (dd, J = 9.0,. 1.2Hz, 1H), 3.93 (s, 3H), 3.09 (q, J = 7.3 Hz, 2H), 1.24 (t, J = 7.3 Hz,3H). 1-1-002 δ 8.85-8.82(m, 1H), 8.72-8.68(m,. 1H), 8.30(d, J = 1.2 Hz,1H), 7.44(d, J = 0.9 Hz, 1 H), 7.47-7.34(m, 2H), 4.38(s, 3H). 1-1-003 δ8.73-8.69(m, 2H), 8.32(s, 1H), 7.56(d, J = 9.0 Hz, 1H), 7.38(s, 1H),7.33-7.26(m, 1H), 4.40(s, 3H). 1-1-004 δ 8.89(s, 1H), 8.71(d, J = 2.1Hz, 1H), 8.32(d, J = 2.1 Hz, 1H), 7.77(d, J = 9.3 Hz, 1H), 7.46(s, 1H),7.36(d, J = 9.3 Hz, 1H). 4.41(s, 3H). 1-10-002 δ 8.85-8.80(m, 1H),8.45-8.40(m, 1H), 8.09(s, 1H), 7.82(d, J = 9.3 Hz, 1H), 7.39(d, J = 9.3Hz, 1H), 4.04(s, 3H). 1-10-004 δ 9.12(s, 1H), 8.96 (s, 1H), 8.14 (s.1H), 8.09 (s, 1H), 7.90 (d, J = 9.2 Hz, 1H), 7.35 (d, J = 9.2 Hz, 1H),4.47 (s, 3H).

Now, usefulness of the compounds of the present invention as pesticideswill be described in detail by referring to the following Test Examples,but the present invention is by no means restricted thereto.

Test Example 1: Insecticidal Test on Nilaparvata lugens

10% emulsifiable concentrates (or 10% wettable powders) of compounds ofthe present invention were diluted with water containing a spreader toobtain 500 ppm solutions. Rice sheaths were soaked in the solutions forabout 10 seconds. After the soaking, the rice sheaths were dried in airand put in test tubes. In each tube, five 3rd-instar larvae ofNilaparvata lugens were released, and the tubes were capped with spongeand placed in an incubator at 25° C. 6 days after, dead insects in thetest tubes were counted, and the mortality was calculated in accordancewith the following equation. The test was carried out in duplicate.

Mortality (%)=(the number of dead insects/the number of releasedinsects)×100)

Among the compounds tested, the following compounds showed a mortalityof at least 90%.

Compounds Nos. 1-1-004a, 1-1-005a, 1-1-013a, 1-1-014a, 1-1-015a,1-2-001a, 1-2-002a, 1-10-001a and 1-11-001a of the present invention.

Test Example 2: Insecticidal Test on Plutella xylostella

10% emulsifiable concentrates (or 10% wettable powders) of compounds ofthe present invention were diluted with water containing a spreader toobtain 500 ppm solutions. Leaves of cabbage were soaked in the solutionsfor about 10 seconds. After the soaking, the leaves were dried in airand placed in dishes. In each dish, five 3rd-instar larvae of Plutellaxylostella were released, and the dishes were covered with lids andplaced in an incubator at 25° C. 6 days after, dead insects in thedishes were counted, and the mortality was calculated by using the sameequation as in Test Example 1. The test was carried out in duplicate.

Among the compounds tested, the following compounds showed a mortalityof at least 90%.

Compounds 1-1-001a, 1-1-002a, 1-1-002b, 1-1-003a, 1-1-004a, 1-1-005a,1-1-006a, 1-1-006b, 1-1-007a, 1-1-008a, 1-1-009a, 1-1-010a, 1-1-011a,1-1-012a, 1-1-012b, 1-1- 013a, 1-1-014a, 1-1-015a, 1-1-016a, 1-1-016b,1-1-017a, 1-2-001a, 1-3-001a, 1-4-001a, 1-5-001a, 1-10-001a, 1-10-003a,1-11-001a and 1-11-001b of the present invention.

TEST Example 3: Insecticidal Test on Spodoptera litura

10% emulsifiable concentrates (or 10% wettable powders) of compounds ofthe present invention were diluted with water containing a spreader toobtain 500 ppm solutions. Leaves of cabbage were soaked in the solutionsfor about 10 seconds. After the soaking, the leaves were dried in airand placed in dishes. In each dish, five 3rd-instar larvae of Spodopteralitura were released, and the dishes were covered with lids and placedin an incubator at 25° C. 6 days after, dead insects in the dishes werecounted, and the mortality was calculated by using the same equation asin Test Example 1. The test was carried out in duplicate.

Among the compounds tested, the following compounds showed a mortalityof at least 90%.

Compounds Nos. 1-1-001a, 1-1-002a, 1-1-002b, 1-1-003a, 1-1-004a,1-1-005a, 1-1-006a, 1-1-006b, 1-1-007a, 1-1-008a, 1-1-009a, 1-1-010a,1-1-011a, 1-1-012a, 1-1-012b, 1-1-013a, 1-1-014a, 1-1-015a, 1-1-016a,1-1-016b, 1-1-017a, 1-2-001a, 1-3-001a, 1-4-001a, 1-5-001a, 1-10-001a,1-10-003a, 1-11-001a and 1-11-001b of the present invention.

Test Example 4: Insecticidal Activity on Frankliniella occidentalis

In styrol cups having an inner diameter of 7 cm, wet filter paper waslaid, kidney bean leaves cut into a 3 cm square were laid on the paper,and each leaf was inoculated with 20 larvae of Frankliniellaoccidentalis. 10% emulsifiable concentrates (or 10% wettable powders) ofcompounds of the present invention were diluted with water containing aspreader to obtain 500 ppm solutions. 2.5 ml of the solutions weresprayed from a rotary spray tower into the styrol cups (2.5 mg/cm²). 2days after, dead insects were counted, and the insect damage degree onkidney bean leaves was examined. The mortality was calculated by usingthe same equation as in Test Example 1. The insect damage degree wasevaluated from the proportion of the area with insect damage on theleaves, as follows. 1: 0 to 20% insect damage, 2: 20 to 50% insectdamage, 3: 50 to 70% insect damage, and 4: 70% or higher insect damage.The test was carried out in duplicate.

Among the compounds tested, the following compounds showed a mortalityof at least 50% and an insect damage degree of 2 or 1.

Compounds Nos. 1-1-002a, 1-1-004a, 1-1-006a, 1-1-006b, 1-1-007a,1-1-008a, 1-1-012a, 1-1-012b, 1-1-013a, 1-1-014a, 1-1-015a, 1-1-016b,1-2-001a and 1-3-001a of the present invention.

Test Example 5: Insecticidal Test on Myzus persicae

Wet absorbent cotton was laid on glass dishes having an inner diameterof 3 cm, and covered with leaves of cabbage cut into circles having adiameter of 3 cm, and 4 apterous adults of Myzus persicae were released.After a day, 10% emulsifiable concentrates (or 10% wettable powders) ofcompounds of the present invention were diluted with water containing aspreader to obtain 500 ppm solutions. The solutions were sprayed from arotary spray tower (2.5 mg/cm²), and the dishes were covered with lidsand placed in an incubator at 25° C. 6 days after, dead insects werecounted, and the mortality was calculated by using the same equation asin Test Example 1. The test was carried out in duplicate.

Among the compounds tested, the following compounds showed a mortalityof at least 90%.

Compounds Nos. 1-1-001a, 1-1-002a, 1-1-002b, 1-1-004a, 1-1-005a,1-1-006a, 1-1-006b, 1-1-007a, 1-1-008a, 1-1-010a, 1-1-011a, 1-1-012a,1-1-012b, 1-1-013a, 1-1-014a, 1-1-015a, 1-1-016a, 1-1-016b, 1-1-017a,1-2-001a, 1-2-002a, 1-10-001a and 1-11-001b of the present invention.

Test Example 6: Soil Irrigation Test on Myzus persicae

10% emulsifiable concentrates of compounds of the present invention werediluted with tap water to obtain 500 ppm solutions.

The soil around the bases of cabbage seedlings (at the 2.5-leaf stage)planted in plastic cups was irrigated with 10 ml of the solutions. Afterthe irrigation, the cabbage seedlings were placed in a greenhouse. Oneday after the irrigation, adults of Myzus persicae were released at aratio of 20 insects per seedling, and the seedlings were left in thegreenhouse. 6 days after the release of the insects, living insects werecounted, and the control value was calculated from the followingequation.

Control value (%)={1−(Cb×Tai)/(Cai×Tb)}×100

Cb: the number of insects in a non-treated plot before treatment

Cai: the final number of living insects in a non-treated plot

Tb: the number of insects in a treated plot before treatment

Tai: the final number of living insects in a treated plot

Among the compounds tested, the following compounds showed a controlvalue of at least 90%.

Compounds Nos. 1-1-004a, 1-1-006a, 1-1-013a, 1-1-014a, 1-1-015a and1-2-001a of the present invention.

Test Example 7: Systemic Insecticidal Test on Nilaparvata lugens

10% emulsifiable concentrates of compounds of the present invention werediluted with tap water to obtain 20 ppm solutions, and root of rice plugseedlings (at the 2-leaf stage) were dipped in the solutions. 7 daysafter, the rice seedlings were picked and put in test tubes, and in eachtube, five 3rd-instar larvae of Nilaparvata lugens were released, andthe tubes were capped with sponge and placed in an incubator at 25° C. 6days after the release of the insects, dead insects were counted, theand the mortality was calculated by using the same equation as in TestExample 1. The test was carried out in duplicate.

Among the compounds tested, the following compounds showed a mortalityof at least 90%.

Compounds Nos. 1-1-001a, 1-1-004a, 1-1-013a, 1-1-014a, 1-1-015a,1-2-001a, 1-4-001a and 1-10-001a of the present invention.

Test Example 8: Soil Irrigation Test on Plutella xylostella

10% emulsifiable concentrates of compounds of the present invention werediluted with tap water to obtain 500 ppm solutions. The soil around thebases of cabbage seedlings (at the 2.5-leaf stage) planted in plasticcups was irrigated with 10 ml of the solutions. After the irrigation,the cabbage seedlings were placed in a greenhouse. 5 days after theirrigation, leaves of cabbage were picked and placed in dishes. In eachdish, five 3rd-instar larvae of Plutella xylostella were released, andthe dishes were covered with lids and placed in an incubator at 25° C. 6days after, dead insects in the dishes were counted, and the controlvalue was calculated by using the same equation as in Test Example 6.The test was carried out in duplicate.

Among the compounds tested, the following compounds showed a controlvalue of at least 90%.

Compounds Nos. 1-1-001a, 1-1-002a, 1-1-004a, 1-1-005a, 1-1-006a,1-1-013a, 1-1-014a, 1-1-015a, 1-2-001a, 1-4-001a and 1-10-001a of thepresent invention.

Test Example 9: Test on the Effect of Seed Treatment on Aphis glycines

2.4 mg of compounds of the present invention were diluted with 97.6 μlof acetone. Four soybean seeds were put in each 50 ml plastic tube, andthe solutions of compounds of the present invention were poured onto theseeds and stirred until the acetone evaporated completely so that theseeds were evenly coated with the compounds. The treated seeds were sownin pots, 4 seeds per pot, and placed in a greenhouse. After the primaryleaf folded out, two adults of Aphis glycines were released perseedling. 7 days after the release of the insects, living insects werecounted, and the control value was calculated by using the same equationas in Test Example 6.

Among the compounds tested, the following compounds showed a controlvalue of at least 90%.

Compounds Nos.: 1-1-004a, 1-1-006a, 1-1-013a, 1-1-014a, 1-1-015a and1-2-001a of the present invention.

Test Example 10: Test on the Effect on Rhipicephalus sanguineus

3.5 mg of compounds of the present invention were diluted with 3.5 ml ofacetone to obtain 1,000 ppm solutions. 350 μl of the solutions wereapplied to the bottoms and the side walls of glass containers with aninner wall surface area of 35 cm², and acetone was volatilized toprepare thin films of the compounds on the inner walls of the glasscontainers. Since the inner wall surface area of each glass containerwas 35 cm², the application dose was 10 μg/cm².

To each glass container, five protonymphs (male and female) ofRhipicephalus sanguineus were released, and the containers were coveredwith lids and placed in an incubator at 25° C. 4 days after the releaseof the ticks, dead ticks were counted, and the mortality was calculatedby using the same equation as in Test Example 1.

Among the compounds tested, the following compounds showed a mortalityof at least 50%.

Compounds Nos. 1-1-001a, 1-1-002a, 1-1-002b, 1-1-004a, 1-1-005a,1-1-007a, 1-1-009a, 1-1-010a, 1-1-012a, 1-1-013a, 1-1-014a, 1-1-015a,1-1-016a, 1-1-016b, 1-1-017a, 1-3-001a, 1-4-001a, 1-5-001a and 1-11-001aof the present invention.

Test Example 11: Test on the Effect on Ctenocephalides felis

3.5 mg of compounds of the present invention were diluted with 3.5 ml ofacetone to obtain 1,000 ppm solutions. 350 μl of the solutions wereapplied to the bottoms and the side walls of glass containers with aninner wall surface area of 35 cm², and acetone was volatilized toprepare thin films of the compounds on the inner walls of the glasscontainers. Since the inner wall surface area of each glass containerwas 35 cm², the application dose was 10 μg/cm².

To each glass container, five adults (male and female) ofCtenocephalides felis were released, and the containers were coveredwith lids and placed in an incubator at 25° C. 4 days after the releaseof the fleas, dead fleas were counted, and the mortality was calculatedby using the same equation as in Test Example 1.

Among the compounds tested, the following compounds showed a mortalityof at least 50%.

Compounds Nos. 1-1-001a, 1-1-002a, 1-1-002b, 1-1-003a, 1-1-004a,1-1-005a, 1-1-006a, 1-1-006b, 1-1-007a, 1-1-009a, 1-1-010a, 1-1-012a,1-1-013a, 1-1-014a, 1-1-015a, 1-1-016a, 1-1-016b, 1-1-017a, 1-2-001a,1-3-001a, 1-4-001a, 1-5-001a, 1-10-001a and 1-11-001a of the presentinvention.

Test Example 12: Test on the Parasiticidal Effect by Rat OralAdministration on Rhipicephalus sanguineus

5 mg of compounds of the present invention were dissolved in 5 ml ofolive oil to prepare administration solutions. The solutions were orallyadministered to rats in a dose of 10 ml/kg body weight by a feedingtube. The oral administration was repeated twice in each group. 1 hourafter the administration, 50 protonymphs (male and female) ofRhipicephalus sanguineus were released for each rat. 3 days after therelease of the ticks, the number of ticks parasitic on the rats werecounted, and the parasiticidal degree was calculated from the followingequation.

Parasticidal degree (%)=100×(1−the number of parasitic ticks onadministered group/the number of parasitic ticks on non-administeredgroup)

Among the compounds tested, the following compounds showed aparasiticidal degree of at least 70%.

Compounds Nos. 1-1-002a, 1-1-004a, 1-1-005a and 1-1-007a of the presentinvention.

Test Example 13: Insecticidal Test on Muca domestica

2 mg of compounds of the present invention were dissolved in 1 ml ofacetone to prepare 2 μg/μl solutions. Female adults of Musca domesticawere anesthetized with carbon dioxide gas, and 1 μl of the solutionswere applied to thorax notum of the insects by a topical applicator(manufactured by Burkard Scientific Ltd.). After the application, theinsects were put in plastic cups with lids having an inner diameter of7.5 cm and a height of 4 cm, and the cups were placed in an incubator at25° C. 3 days after, dead insects in the cups were counted, and themortality was calculated by using the same equation as in TestExample 1. The test was carried out in duplicate with 5 insects.

Among the compounds tested, the following compounds showed a mortalityof at least 70%.

Compounds Nos. 1-1-001a, 1-1-002a, 1-1-006a, 1-1-007a, 1-10-001a and1-2-001a of the present invention.

Test Example 14: Insecticidal Test on Blattela germanica

2 mg of compounds of the present invention were dissolved in 0.2 ml ofacetone to prepare 10 μg/μl solutions. Male adults of Blattela germanicawere anesthetized with carbon dioxide gas, and 1 μl of the solutionswere applied to abdomens of the insects by a topical applicator(manufactured by Burkard Scientific Ltd.). After the application, theinsects were put in deep dishes having an inner diameter of 6 cm and aheight of 6 cm, and the dishes were placed in an incubator at 25° C. 3days after, writhing insects and dead insects were counted, and thewrithing/dead insects ratio (%) was calculated from the followingequation. The test was carried out in quadruplicate with 5 insects.

Writhing/dead insects ratio (%)=(the number of writhing insects+thenumber of dead insects)/the number of insects tested×100

Among the compounds tested, the following compounds showed awrithing/dead insects ratio of at least 70%.

Compounds Nos. 1-1-001a, 1-1-002a, 1-10-001a and 1-2-001a of the presentinvention.

Test Example 15: Insecticidal Test on Reticulitermes speratus

10% emulsifiable concentrates of the compounds of the present inventionwere prepared. The emulsifiable concentrates were diluted with water toprepare 100 ppm solutions. 0.5 ml of the solutions were dropped on 10 gof river sand and mixed. In dishes having an inner diameter of 4 cm, 1%agar (2 cm square) was laid, and the treated river sand and a filterpaper piece as bait were placed. Adults of Reticulitermes speratus werereleased in the dishes, and the dishes were placed in an incubator at25° C. 10 days after, dead insects in the dishes were counted, and themortality was calculated by using the same equation as in TestExample 1. The test was carried out in duplicate.

Among the compounds tested, the following compounds showed a mortalityof at least 70%.

Compound Nos. 1-1-001a, 1-1-002a, 1-1-006a, 1-1-007a, 1-10-001a and1-2-001a of the present invention.

Test Example 16: Insecticidal Test on Culex pipiens molestus

2 mg of compounds of the present invention were dissolved in 0.2 ml ofdimethyl sulfoxide to prepare 1% (w/v) dimethyl sulfoxide solutions. Thesolutions were diluted with distilled water by a factor of 100 toprepare 100 ppm solutions. To 1.9 ml plastic plates (Cellstar 24 wellplate, manufactured by Greiner Bio-One International GmbH) as testplates, 0.7 ml of water containing 10 to 30 larvae of Culex pipiensmolestus one day after hatching, and 0.2 ml of an aqueous suspension ofaquarium fish food (TetraMin manufactured by Spectrum Brands Japan) asbait, were dropped. 0.1 ml of the 100 ppm solutions were dropped, andthe plates were placed in an incubator at 25° C. 1 day after, deadlarvae were counted, and the mortality was calculated by using the sameequation as in Test Example 1. The test was carried out in duplicate.

Among the compounds tested, the following compounds showed a mortalityof 100%.

Compound Nos. 1-1-001a, 1-1-002a, 1-1-006a and 1-1-007a of the presentinvention.

Test Example 17: Insecticidal Test on Aedes albopictus

2 mg of compounds of the present invention were dissolved in 0.2 ml ofdimethyl sulfoxide to prepare 1% (w/v) dimethyl sulfoxide solutions.0.01 ml of the solutions were mixed with 0.99 ml of pure water toprepare 0.01% (w/v) solutions. To 0.3 ml plastic plates (Cellstar 96well culture plates, manufactured by Greiner Bio-One International GmbH)as test plates, 0.09 ml of distilled water containing 30 larvae of Aedesalbopictus one day after hatching was dropped, and 0.01 ml of the 0.01%(w/v) solutions were dropped so that the final concentration would be 10ppm. The plates were covered with lids and placed in an incubator at 25°C. 3 days after, dead larvae were counted, and the mortality wascalculated by using the same equation as in Test Example 1.

Among the compounds tested, the following compounds showed a mortalityof at least 70%.

Compound Nos. 1-1-001a, 1-1-002a, 1-1-003a, 1-1-004a, 1-1-005a,1-1-006a, 1-1-006b, 1-1-007a, 1-1-010a, 1-1-011a, 1-1-013a, 1-1-016b,1-2-001a, 1-2-002a, 1-2-002b, 1-3-001a, 1-4-001a, 1-5-001a, 1-11-001aand 1-11-001b of the present invention.

INDUSTRIAL APPLICABILITY

The compounds of the present invention are very useful as novelpesticides which have excellent pesticidal activities, which have littleharmful effect on non-target organisms such as mammals, fishes anduseful insects, which have low toxicity, and which have low persistence.

The entire disclosures of the following Japanese Patent Applicationsincluding specification, claims, drawings and summary are incorporatedherein by reference in their entireties.

JP-A-2016-047064 (Mar. 10, 2016)

JP-A-2016-054191 (Mar. 17, 2016)

JP-A-2016-199515 (Oct. 7, 2016)

JP-A-2016-255131 (Dec. 28, 2016)

1-7. (canceled) 8: The condensed heterocyclic compound or its salt, orN-oxide thereof having the formula (1-4):

wherein A⁸ is a nitrogen atom, R¹ is C₁-C₆ alkyl, R⁷ is halo (C₁-C₆)alkyl, R⁶ is hydrogen or C₁-C₆ alkyl, Y1 is a hydrogen atom or a halogenatom, N is an integer of 0, 1, or 2 and each of Y2, Y3 and Y4 isindependently a hydrogen atom, a halogen atom, halo (C₁-C₆) alkyl, C₁-C₆alkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ alkylsulfonyl, G1 or G2. 9: Thecondensed heterocyclic compound or its salt, or N-oxide thereofaccording to claim 8, wherein R⁶ is a hydrogen atom, each of Y1, Y3 andY4 is a hydrogen atom, Y2 is halo (C₁-C₆) alkyl, and n is an integer of2. 10-11. (canceled) 12: A pesticide, comprising at least one condensedheterocyclic compound or a salt thereof according to claim 8, as anactive ingredient. 13: An agricultural chemical, comprising at least onecondensed heterocyclic compound or a salt thereof according to claim 8,as an active ingredient. 14: A parasiticide against internal or externalparasites in or on a mammal or bird, comprising at least one condensedheterocyclic compound or a salt thereof according to claim 8, as anactive ingredient. 15: The parasiticide according to claim 14, whereinthe external parasites are Siphonaptera or ticks. 16: An insecticide oracaricide, comprising at least one condensed heterocyclic compound or asalt thereof according to claim 8, as an active ingredient. 17: A soiltreatment agent, comprising at least one condensed heterocyclic compoundor a salt thereof according to claim 8, as an active ingredient. 18: Asoil treatment method, comprising treat soil with the soil treatmentagent according to claim 17, by irrigation. 19: A seed treatment agent,comprising at least one condensed heterocyclic compound or a saltthereof according to claim 8, as an active ingredient. 20: A seedtreatment method, comprising treating seeds with the seed treatmentagent according to claim 19 by dipping.